CHAPTER 4-ENERGY BALANCE

FOR NONREACTIVE SYSTEM

CHE243-MATERIAL AND ENERGY BALANCE AND
SIMULATION

Forms of Energy
Three component of total energy of a system
Kinetic energy (Ek)

Potential energy (Ep)

energy due to the translational motion of the system as a whole

relative to some frame of reference (usually the earths surface)
or to rotation of the system about some axis.
energy due to the position of the system in a potential field
(such as a gravitational or electromagnetic field).

Internal energy (U)

all energy possessed by a system other than kinetic and

potential energy; or
Energy due to translation, rotation, vibration &
electromagnetic interactions of the molecules, atom and
subatomic particle within the system.

Transfer of Energy

In closed system (i.e. no mass is transferred across the

system boundaries while the process is taking place),
energy may be transferred between such a system and its
surroundings in two ways as heat or work.
Heat

Energy that flows as a result of temperature difference between

a system and its surroundings.
The direction of flow is always from a higher temperature to a
low one.
Heat is defined as positive when its transferred to the system
from the surroundings.

Work

energy that flows in response to any driving force other a

temperature difference, such as a force, a torque or a voltage
Work is defined as positive when it is done by the system on
the surroundings.

First Law of Thermodynamics

Law

of conservation of energy, which state that energy can

neither be created nor destroyed.

General

form of first law of thermodynamics

Inlet Energy + Heat - Outlet Energy Work = Accumulation
Inlet energy and outlet energy is summation/total of all
energy such as potential, kinetic and internal energy

Kinetic Energy Equation (Ek)

Kinetic energy, Ek (J) of an object of mass m (kg) moving

with velocity u (m/s) relative to the surface of the earth is

1
2
E k mu
2

(kg/s)
If the fluid enters a system with a mass flow rate m
and uniform velocity u (m/s), the rate at which kinetic
energy (J/s) is transported into the system is

E k m u 2
2

Potential Energy Equation (Ep)

Gravitational potential energy, Ep

E p mgz

if the fluid enters a system with a mass flow rate m

(kg/s)
and an elevation z relative to the potential energy
reference plane.

gz
Ep m

Normally we are interested in the change of potential

energy during energy balance calculation

g ( z 2 z1 )
E p E p 2 E p1 m

Energy Balances on Closed System

Closed system
no mass is transferred across the system boundaries while the
process is taking place

Energy balance
Final System Energy Initial System Energy

= Net Energy Transferred to the System

Initial energy system

= Ui + Eki + Epi

Final energy system = Uf + Ekf + Epf

Net energy transfer

= Q-W

(Uf-Ui) + (Ekf-Eki) + (Epf-Epi) = Q-W

U Ek E p Q W

Energy Balances on Closed System

When applying energy balance equation to a given process, the following

point must be aware;
1. The internal energy of a system depends almost entirely on the
chemical composition, state of aggregation (solid, liquid, or gas), and
temperature of the system materials. If no temperature changes, phase
changes, or chemical reactions occur in a closed system and if pressure
changes are less than a few atmospheres, then U 0.
2.

If a system is not accelerating, then Ek = 0. If a system is not rising or

falling, then Ep = 0.

3.

If a system and its surroundings are at the same temperature or the

system is perfectly insulated, then Q = 0. The process is then termed
adiabatic.

4.

Work done on or by a closed system is accomplished by movement of

the system boundary against a resisting force or the passage of an
electrical current or radiation across the system boundary. If there no
moving parts or electrical current at the system boundary, then W = 0.

Energy Balances on Open System

In open system, mass is transferred across the system

boundaries while the process is taking place.
Therefore work must be done on open system to push mass in
and work is done on the surrounding by mass that emerges
from the systems.
Both work terms must be include in the energy balance for
open system
The net work done by an open system

W Ws W fl
W s - shaft work

- rate of work done by the process fluid on a moving part

within the system such as a pump rotor.
W fl - flow work
- rate of work done by the fluid at the system outlet
minus
rate of work done by the fluid at the system inlet.

Energy Balances on Open System

^ symbol is used to denote the specific property ( property

divided by mass or by mole) such as specific internal
energy ( kJ/kg), specific volume (m3/kg) and so on.

One important property for energy balance on open system

is specific enthalpy ( kJ/kg).

H U PV

Sometimes, universal gas law constant can be used as a

conversion factor to evaluate specific enthalpy.

Energy Balances on Open System

The first law of thermodynamics for an open system

at steady state
input=output
Q E j E j W
input

output

Upon derivation, the equation reduced to,

H E k E p Q Ws

If a process has a single input and output stream, the

expression forH simplifies to
( H out H in ) m
H
H m

ENERGY balance for non reactive system

Reference State

A common practice is to arbitrarily designate a reference state for a

substance at which U or H is declared to equal zero, and then tabulate
U and/or H for the substance relative to the reference state. *Note: Refer
Felder pp. 339 and 359

In Chapter 7 (Felder), U and H are state properties of a species; their

values depend only on the state of the species primarily on its
temperature and state of aggregation (solid, liquid or gas) and, to a
lesser extent, on its pressure (and for mixtures of some species, on its
mole fraction in the mixture).
When a species passes from one state to another, both U and H for
the process are independent of the path taken from the first state to
second one Hypothetical Process Path *Note: Refer Felder pp. 360

HYPOTHETICAL PROCESS PATHS

CHANGES IN
P AT
CONSTANT T

CHANGES IN
T AT
CONSTANT P

PHASE
CHANGE
OPERATIONS

CHANGES IN P AT CONSTANT T

Internal energy (U) is nearly independent of pressure for solids and

liquids at a fixed temperature, as is specific volume (V) . *Note: Refer
Felder pp. 365 366

If pressure of a solid and liquid changes at constant temperature

U = 0
H = [U + (PV)] = [U + PV + V P] = [V P]

Both U and H independent of pressure for ideal gases may assume

U = 0 and H = 0 for a gas undergoing an isothermal pressure change
unless gas temperature below 0 0C or well above 1 atm are involved.

CHANGES IN TEMPERATURE

SENSIBLE
HEAT AND
HEAT
CAPACITIES

HEAT
CAPACITY
FORMULAS

ESTIMATION
OF HEAT
CAPACITIES

SENSIBLE HEAT AND HEAT CAPACITIES

The term sensible heat signifies that heat must be transferred to raise
or lower the temperature of a substance or mixture of substances.
*Note: Refer Felder pp. 366
The quantity of heat required to produce a temperature change:
Q = U

(closed system)

Q = H

(open system)

Heat capacity at constant volume Cv. At constant volume:

T2

U Cv T dT
^

T1

SENSIBLE HEAT AND HEAT CAPACITIES

Suppose both temperature and the volume of a substance change. To

calculate U break the process into 2 steps ( a change in V at
constant T followed by a changes in T and constant V):

AT1 ,V1
AT1 ,V2
AT2 ,V2
^

U 1

U 2

U U 1 U 2

SENSIBLE HEAT AND HEAT CAPACITIES

For ideal gas and (to a good approximation) liquid and solids, U
depends only on T. In step 1, T is constant, U1 = 0.
Step 2 V is constant:

T2

U Cv T dT
^

T1

Ideal gas: Exact

Solid or liquid: good approximation
Non ideal gas: valid only if V is constant

SENSIBLE HEAT AND HEAT CAPACITIES

Heat capacity at constant pressure Cp. At constant pressure:

T2

H C p T dT
^

T1

For first step refer section 8.2 (Felder), as T is constant, H1 = 0 (for

ideal gas), H1 = V P (for solid or liquid).
Step 2 P is constant:
T2

H VP C p T dT
^

T1

Solid or liquid

T2

H C p T dT
^

T1

Ideal gas: Exact

Non ideal gas: valid only if P
is constant

Example
Calculate the heat required to raise 200 kg nitrous oxide from 200C to
1500C in a constant volume vessel. The constant volume heat
capacity in this temperature range is given by the equation:

Cv kJ/kg0 C 0.855 9.42 10 4 T

where T in 0C
Answer
^

U 24 312 kJ

HEAT CAPACITY FORMULAS

Heat capacities are functions of temperature and frequently expressed

in polynomial form (Cp = a + bT + cT2 + dT3). *Note: Refer Felder pp. 369

Liquid and Solids : C p C v

Ideal Gases

: C p Cv R
R: Gas constant

Example (Felder pp369)

Assuming ideal gas behavior, calculate the heat must be transferred in
each of the following cases.

1.

A stream of nitrogen flowing at a rate of 100 mol/min is heated

from 200C to 1000C

2.

Nitrogen contained in 5 liter flask at an initial pressure of 3 bar

is cooled from 900C to 300C

Neglect the changes in kinetic energy

Answer
nH
233.3 kJ
Q

H
1.
min
^

2. Q U n U 0.621 kJ

ESTIMATION OF HEAT CAPACITIES

Kopps rule simple empirical method for estimating the heat

capacity of a solid or liquid near 200C. *Note: Refer Felder pp. 372
Use Data in Table B.10 for Cp of atom compound
Example: heat capacity of solid Ca(OH)2

C pa

26 217 29.6

p Ca OH
2

p Ca OH
2

Ca

True value is 89.5

2 C pa

J
mol0 C

2 C pa

J
J

79
mol0 C
mol0 C

ESTIMATION OF HEAT CAPACITIES

For heat capacities of certain mixture may use these rules:

Rules 1 : For a mixture of gases or liquids, calculate the total enthalpy

change as the sum of the enthalpy changes for the pure mixture
component
Rules 2 : For a highly dilute solutions of solids or gases in liquids,
neglect the enthalpy change of solute.

ESTIMATION OF HEAT CAPACITIES

For heat capacities of certain

mixture: (Cp)mix (T)

C T y C T
p mix

pi

all
mixture
components

where

heat capacity of mixture

yi

massor mole fraction of i component

C pi

heat capacity of i component

p mix

For enthalpy
calculation:
^

C T dT

T2

p mix

T1

Example (Felder pp373)

Calculate the heat required to bring 150 mol/h of a stream containing
60% C2H6 and 40% C3H8 by volume from 00C to 4000C.
Answer

H
n H
5230 kJ
Q
h

PHASE CHANGE OPERATIONS

1)

Latent Heats

Latent heat the specific enthalpy change associated with the

transition of a substance from one phase to another at constant
temperature and pressure. *Note: Refer Felder pp. 378
Latent heats for the two most commonly encountered phase changes
are defined as follows:

1.

Heat of fusion (or heating of melting) Hm (T,P) specific

enthalpy difference between the solid and liquid forms of a
species at T and P

2.

Heat of vaporization Hv (T,P) specific enthalpy

difference
between the liquid and vapor forms of a species at T and P

PHASE CHANGE OPERATIONS

2)

Estimation and Correlation of Latent Heats

Troutons rule a simple formula for estimating a standard heat of
vaporization (Hv at normal boiling point); provide an estimate of Hv
accurate to within 30%. *Note: Refer Felder pp. 381

H v (kJ/mol) 0.088Tb (K) nonpolar liquids

0.109Tb (K) water, low molecular weight alcohols
Tb : normal boiling point of the liquid

PHASE CHANGE OPERATIONS

2)

Estimation and Correlation of Latent Heats

Chens equation provides roughly 2% accuracy. *Note: Refer Felder
pp. 381

H v (kJ/mol)

Tb 0.0331Tb Tc 0.0327 0.0297 log10 Pc

1.07 Tb Tc

Tb : normal boiling point (K)

Tc : critical temperatur e (K)
Pc : critical pressure (atm)

PHASE CHANGE OPERATIONS

2)

Estimation and Correlation of Latent Heats

A formula for approximating a standard heat of fusion. *Note: Refer
Felder pp. 381
^

H m (kJ/mol) 0.0092Tm (K) metallic elements

0.0025Tm (K) inorganic compounds
0.050Tm (K)

organic compounds

Tm : normal melting point of the solid

PHASE CHANGE OPERATIONS

2)

Estimation and Correlation of Latent Heats

Watsons colleration a useful approximation for estimating Hv at T2
for known value at T1. *Note: Refer Felder pp. 382

T T2

H v (T2 ) H v (T1 ) c
Tc T1
Tc : critical temperatur e
^

0.38

Example (Felder pp379)

100 mole/h of liquid n-hexane (C6H14) at 250C and 7 bar is vaporized
and heated to 3000C at constant pressure. Neglecting the effect of
pressure on enthalpy, estimate the rate at which heat must be supplied.
Given the boiling temperature of n-hexane at 7 bar is 1460C. Use data
provided in Table B.1 to solve the problem.

Q 2.38 kW

ENERGY balance for non reactive system

PROCEDURE
CALCULATION

SIMPLE
ENERGY
BALANCE
CALCULATION

MIXING AND
SOLUTION

PROCEDURE CALCULATION

Perform all required material balance calculation. *Note: Refer Felder

pp. 361
Write the appropiate form of energy balance (close or open system)
and delete any terms that are either zero or negligible for given
process system.

Choose a reference state phase, temperature and pressure for each

species involved in the process
Construct inlet outlet enthalpy table (open system) or inlet outlet
internal energy table (close system)

PROCEDURE CALCULATION

Calculate all required values (U or H) and insert the values into

appropriate table
Calculate Q for open or close system
Close system : U

nU nU
i

final

Open system : H

initial

n H n H
i

final

or miU i miU i

initial

out

in

or mi H i mi H i
out

in

Calculate any work, kinetic energy or potential energy terms not

dropped from energy balance
Solve the energy balance for unknown variables

SIMPLE ENERGY BALANCE CALCULATION

Example Energy balance on a gas preheater (Felder pp374)
A stream containing 10% methane (CH4) and 90% air by volume is to be
heated from 200C to 3000C. Calculate the required rate of heat input in
kW if the flow rate of the gas is 2.00 x 103 liters (STP)/min

Q 12.93

kJ
@ 12.93 kW
s

SIMPLE ENERGY BALANCE CALCULATION

Example Partial vaporization of mixture (Felder pp383)
An equimolar mixture of benzene (B) and toluene (T) at 100C is fed
continuously into an evaporator which the mixture is heated to 500C.
The liquid product is 40 mole% B, and the vapor product is 68.4 mole%
B. Given the vapor pressure of product is 34.8 mm Hg. Neglecting the
effect of pressure on enthalpy, estimate the heat must be transferred to
the mixture per g-mole of feed.

Q 17.7 kJ

MIXING AND SOLUTION

Heat of mixing and solution can be analyzed when 2

different liquids are mixed or when a gas or solid is
dissolved in a liquid.
Heat of solution, H s (T , r ) - enthalpy change for a process
in which 1 mole of a solute (gas/solid) is dissolved in r
moles of a liquid solvent at constant T
As r become large, H s approach a limiting value known
as heat of solution at infinite dilution
Heat of mixing has the same meaning as the heat of
solution when the process involves mixing two fluids

MIXING AND SOLUTION

Example production of hydrochloric acid (Felder pp397)
Hydrochloric acid is produced by absorbing gaseous HCl (hydrogen
chloride) in water. Calculate the heat that must be transferred to or
from an absorption unit if HCl(g) at 100C and H2O(l) at 25C are fed to
produce 1000kg/h of 20wt% HCl(aq) at 40C

Q 3.35 10 5 kJ/h