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BKF2343
MATERIAL AND ENERGY
BALANCE

Sem II 2016/2017Energy
Balance

Chapter 5:
Energy Balance on
Nonreactive System
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Topic Outcomes
 Construct hypothetical process path for each species involved in
chemical process.

 Solve for the internal energy change ΔU (closed system) or enthalpy

change ΔH (open system) based on the changes in states (i.e.
temperature, pressure and phase) in chemical processes.

 Construct an enthalpy table and perform energy balance calculations

for nonreactive process.
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CONTENT

Methods to calculate ΔĤ
and ΔÛ associated with
certain processes such as:
Change in P, at
constant T &
Hypothetical Process constant phase Procedure of Energy
Path Change in T, at Balance Calculations
constant P &
constant phase
Phase changes at
constant T &
constant P
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INTRODUCTION
  In previous chapter, we saw that the energy balance equations are:

 If we have tables of specific internal energies and enthalpies as we

do for water in the steam tables, calculating ∆U, ∆ is straightforward.
 This chapter discusses how to do it if we don’t have those tables.
+ State Properties and Hypothetical Process Path 5

 State properties
 properties that depend on the state of the species (phase,
temperature and pressure).
 Specific enthalpy (Ĥ) and specific internal energy (Û) are state
properties.
 When a species passes from one state to another state, both ΔĤ and
ΔÛ for the process are independent of the path taken from the first
state to the second state.

 Hypothetical process path

 a path consist of several steps based on our convenience, as long as we
reach to the final state starting from their initial state.
 ΔÛ or ΔĤ for each step in the hypothetical process path is determined.
+ Hypothetical Process Path 6

Example: Calculate ΔĤ for a process in which solid phenol at

25˚C, 1 atm is converted to phenol vapor at 300˚C, 3 atm

 If we have table of enthalpies for phenol,

ΔĤ= Ĥ2 (vapor, 300˚C, 3 atm) – Ĥ1 (solid, 25˚C, 1 atm)

 However, cannot determine directly form enthalpy table (no

table enthalpies for phenol). Thus have to construct a
hypothetical path.
 Take the initial state (solid, 25˚C, 1 atm) as the reference
state.
 Construct the hypothetical process path from the (initial)
reference state (solid, 25˚C, 1 atm) until reach the final
state (vapor, 300˚C, 3 atm)

ΔĤ=(solid, 25˚C, 1 atm) --> (vapor, 300˚C, 3 atm)

+ Hypothetical Process Path 7

Example: Calculate ΔĤ for a process which from a reference

state; solid phenol at 25˚C, 1 atm to its final state; phenol
vapor at 300˚C, 3 atm

ΔĤ=(solid, 25˚C, 1 atm) --> (vapor, 300˚C, 3 atm)

 Check Table B.1 : P= 1 atm; Tm= 42.5°C and Tb= 181.4°C

True Path
Phenol (s, 25°C, 1 atm) Ph (v, 300C, 3 atm)
Ĥ
Change T, Constant P & Phase Ĥ 1
Ph (s, 42.5°C, 1 atm) Change P, Constant T & Phase
Ĥ 6
Change Phase, Constant P & T Ĥ m
Ph (l, 42.5C, 1 atm) Ph (v, 300C, 1 atm)

Change T, Constant P & Phase Ĥ 3 Ĥ 5 Change T, Constant P & Phase
Ĥ v
Ph (l, 181.4C, 1 atm) Ph (v, 181.4C, 1 atm)
Change Phase, Constant P & T

Hˆ  Hˆ 1  Hˆ m  Hˆ 3  Hˆ v  Hˆ 5  Hˆ 6

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Exercise
 Construct a hypothetical path for the following process:

Cyclohexane vapor at 180°C and 5 atm is cooled and condensed to

liquid cyclohexane at 25°C and 5 atm.
+ Calculating ΔĤ and ΔÛ for the change in a state
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 Determine ΔÛ or ΔĤ for each step in the hypothetical

path:
1. Changes in P at constant T and phase
2. Changes in T at constant P and phase
3. Changes in phase at constant T, P
4. Chemical reaction at constant T, P (∆Hrxn) (Reactive Energy
Balance)
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Change in P at Constant T & Constant Phase

1. Solid & Liquid

- nearly independent of pressure

Uˆ  0
Hˆ  VˆP

2. Ideal Gases
Uˆ( unless
-independent of pressure  0 undergo very large
pressure changes)
ˆ 0
H
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Exercise
 Calculate ΔĤ for a process which the pressure of liquid
acetone is changed from 5 atm to 1 atm at a constant
temperature (20˚C).
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Change in T at Constant P & Constant Phase

 Specific enthalpy change

T2
ˆ
H   C p (TIdeal
)dT gas : exact
T1
Nonideal gas : valid only if V is constant

 Specific internal energy change

T2
Uˆ   C v (T )dT
T1
+ Heat capacity, Cp and Cv
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 Cp - heat capacity at constant pressure

- given in Table B.2 in the form of polynomial
equation function of temperature
 Cv- heat capacity at constant volume

 Relationship between Cp and Cv:

Cv  C p Liquid & Solid
Cv  C p  R Ideal Gas
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Table B.2: Heat Capacities (Cp)

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Exercise
 Calculate the heat that must be transferred in when a stream
of N2 flowing at a rate of 100 mol/min is heated from 20°C to
100°C.
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+ Table B.8 and B.9: Specific Enthalpies of Selected Gases 17
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Exercise
 Calculate the heat that must be transferred in when a stream
of N2 flowing at a rate of 100 mol/min is heated from 20°C to
100°C (Use Table B.8).
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Exercise
 15 kmol/min of air is cooled from 430°C to 100°C. Calculate
the required heat removal rate using :

(1) Table B.2

(2) Table B.8
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Change in Phase at Constant T & Constant P

 Latent heat
 Enthalpy change associated with a phase transition at constant
temperature and pressure (melting, vaporization, sublimation)

 Latent heat of vaporization (heat of vaporization), latent heat of

melting (heat of melting)
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 Heat melting, ΔĤm (T,P)
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 Specific enthalpy different between solid and liquid forms of

species at T & P

 Heat of vaporization, ΔĤv (T,P)

 Specific enthalpy different between liquid and vapor forms of
species at T & P
+ Recall Table B.1 for Heat of Vaporization and Heat of Melting
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Exercise
 100 gmol/h liquid n-hexane at 25°C and 7 bar is vaporized
and heated to 300°C at constant pressure. Estimate the rate
at which heat must be supplied.
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 Nonreactive Energy Balance Procedure: 26

Draw and label the flowchart

Include state information (phase, T,P) in the labeling, and label Q and W or Ws unless you know
they equal to zero

Perform material balance calculations

Write and simplify the energy balance

Choose reference states for each species in the system for and calculations.

For a gaseous species listed Otherwise, choose the species in

For water, if you
in Table B.8, choose the one of its feed or product states,
plan to use steam
species at 25oC and 1 atm so you can set at least one
tables, choose H2O specific internal energy or
(the reference state used in (l, triple point).
Table B.8). enthalpy equal to zero
+Prepare an inlet-outlet internal energy table or enthalpy table. The enthalpy table is 27

shown below as an illustration.

 Solve material balance and include in enthalpy table.

 If a species exists in liquid and vapor phase, include the species with
different phase for its flow rate and enthalpy.
 If the inlet or outlet state is chosen for the reference state of a
species, set its inlet or outlet state enthalpy as zero.
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Calculate all the specific enthalpies based on reference state

Calculate Q= ∑ni Ĥi (final or outlet) - ∑ni Ĥi (initial or inlet)

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Exercise
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SOLUTION:
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Problem from your textbook

Problem 8.52 page 419
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Problem from your textbook

Problem 8.22 page 413
+ Exercise 37

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 kW if the flow rate of the gas is 2 x 103
liter (STP)/min.
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Exercise
 An equimolar liquid mixture of benzene and toluene at 10°C
is fed continuously to a vessel in which the mixture is heated
to 50°C. The liquid products is 40 mole% B and the vapor
products is 68.4% B. How much heat must be
transferred to the mixture per gmole of feed?
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