CHAPTER 4

Energy Balances

Outcome
At the end of this chapter, you are be able
to:
Apply the basic principles of chemical
engineering in energy balance

Chapter Contents
1. Energy Balance Terminology
2. Types of Energy
3. Energy balance: close and open system
4. Energy balance: Reactive and non reactive
system.

Energy Balance Terminology

What is energy?
Energy is the capacity to do work or to produce heat.

Energy has unit of force x distance which are Joules

(N.m), ergs (dyne.cm) and ft.Ibf.

Energy Balance
Terminology

System & Surrounding

In thermodynamic;
a. The system the part of the world in which we have a special
interest (the specific part of the universe).
b. The surroundings the part of the universe outside the
boundary of the system & where the observations are made.
There are 3 type of systems :
a. Open system can exchange both mass & energy with its
surrounding & hence can undergo changes in composition
(cross the boundaries).
b. Closed system can exchange energy but not mass with its
surrounding.
c. Isolated system can not exchange both energy & mass with its
surrounding.

Energy Balance Terminology

System
Surroundings
Boundary
Open system (flow system)
Closed system (unflow system)
Property
State
Steady-state
Phase
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Energy Balance Terminology

Adiabatic system
Isobaric system
Isochoric system
Isothermal system

There are 3 types of energy :

i. Kinetic (Ek)
ii. Potential (Ep)
iii. Internal (U)
Kinetic Energy (Ek)
Kinetic energy (Ek) energy due to the motion of the system
relative to the reference plane.

This energy depend to the velocity, which is dx/dt

Ek = kinetic (motion) energy = (1/2) m2 = (1/2) m2

where m = mass (kg) or m =

mass flowrate (kg/s) & = velocity of
the system (m/s) & the unit of Ek N.m = J or N.m/s = J/s = W.

Potential Energy (Ep)

Potential Energy (Ep) is obtained from the position of the system
within its field.
Ep of the system depend to its relative height in a gravitational
field.

Ep = potential (position in external field) = mgz = mgz

where m = mass (kg) or m = mass flowrate (kg/s), g = gravity

acceleration (m/s) & z = height of the object above a reference
plane.
Internal Energy (U)
Internal energy (U) is the sum of molecular potential and kinetic
energies within a molecular species.

The form of U are :

a. The kinetic energy of the molecules.
b. The potential energy of the constituents of the system.
c. The internal energy stored in the form of the molecular vibration
rotations.
This energy depends to chemical composition, phase condition &
temperature (T). But it not depend to the pressure (P) especially
for liquid & solid. U can not be measured directly but it is possible
to measure the U change, thus :
U = Uf Ui

Heat (Q) & Work (W)

Heat energy (Q) transferring of energy due to the T difference
between the system & its surrounding (from Thigh Tlow).

Almost all chemical rxns absorb and release energy (heat).

Thus, when describing the energy changes during the process,
use term heat released or heat absorbed.
Heat, Q is defined as :
a. + when it is transferred to the system from the surrounding or
any rxn absorbs heat (endothermic).
b. when it is transferred to the surrounding from system or any
rxn release heat (exothermic).
c. 0 when the system is adiabatic (if the system is isolated well).
There is another set of units based on heat :
a. Calorie (cal) = heat needed to raise 1 g of water by 1C/K.
b. Kilocalorie (kcal) = heat needed to raise 1 kg of water by 1C/K.
c. British Termal (Btu) = heat needed to raise 1 Ib of water by
1R/F.

Work Energy (W) the energy flows in response to any driving

force, torque & voltage.
W is defined as force, F multiplied by the distance, d ;
W = F x d

or when deal with external atmospheres pressure, P, the work on

the surrounding :
W = P dV

W is define as :
a. when work is done on the surrounding by the system
b. + when work is done on a system by the surrounding

Energy balance: Close and open system

CLOSED SYSTEM
Closed : Mass is not transferred across the boundaries.
Example :
Batch system

From equation 4.2-1 (pg 85), the generation & consumption

are dropped out energy can neither be created nor
destroyed.
Thus,
Accumulation (change) = input output
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Energy balance: Close and open system

In deriving the integral mass balance for a closed
system, input & output terms are eliminated
No mass crosses the boundaries of a closed system.
However, for energy, heat & work can be transferred.
In energy balance, the accumulation term = value, f
value,I
Final system initial system =

net energy transferred to

system (in out)

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Qty of system energy :

i. Initial system energy = Ui + Eki + Epi

ii. Final system energy = Uf + Ekf + Epf

iii. Energy transferred = Q W

where Q = heat transferred to the system from its

surroundings

W = work done by the system on its surrounding

U/ Ek / Ep = final value initial value. Thus:

U + Ek + Ep = Q W
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OPEN SYSTEM

Open : Mass can be transferred across any of boundaries.

Example : Semibatch & continuous system.
feed
product

5.3.1 Flow Work & Shaft Work

The net rate of work done by an open system on its surroundings
may be written as :
W = Ws + Wfl
where Ws = shaft work or rate of work done by the process fluid on
a moving part within the system (e.g. pump rotor) &

Wfl = flow work or rate of work done by the fluid at the system outlet
the rate of work done on the fluid at the system inlet.
To derive an expression for Wfl, consider the single-inlet-outlet
system shown below:

Vi (m3/s)
Pi (N/m )
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PROCESS

Vo (m3/s)
Po (N/m2)

The fluid enters the system

has work done on it by the fluid just

behind it at rate :

Win (N.m/s) = Pin(N/m2) Vin(m3/s)

While the fluid leaving the system performs work on the
surroundings at a rate :

Wfl = Wout Win

Thus, the net rate at which work is done by the system at the inlet
& outlet is :

Wfl = Pout Vout PinVin or Wfl = (PV)

Thus it can be written as :

W = Ws + (PV)

Specific Properties & Enthalpy

Specific property : Intensive qty (not depend on size of the system)
obtained by dividing an extensive property (depend on size of the
system) by total amount of the process material.
Example : If the volume of a fluid is 200 cm3 & the mass of the fluid
^
is 200 g the specific volume (V) of the fluid is 1 cm3/g.

Use the symbol ^ to denote a specific properties.

^

Example : V = specific volume & U = specific internal energy.

^

For internal energy, U (J) = m (kg) x U (J/kg) & for internal

^
^ at
energy

rate, H (J/s) = m (kg/s) x U (J/kg).

^ energy
^
A property occurs in the
balance equation for open
system
^

is the specific enthalpy, H. H is defined as :

^

H = U + PV
where P is the total pressure, U & V are specific internal energy
&
specific volume.

The Steady State Open-System Energy Balance

At steady state, the open system energy balance is given by:
In = Out

or

H + Ek + Ep = Q Ws

If a process has a single inout & output stream & there is no acc
of mass in the system (min = mout = m). The expression for H

H = m (Hout Hin) = m H

Exercise 1
How would you simplify above equation in each of
the following cases?
There are no moving parts in the system.
The system and its surroundings are at the same
temperature.
The linear velocities of all streams are the same.
All streams enter and leave the process at a single
height

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Exercise 2
The specific internal energy of a fluid is 200 cal/g.
What is the internal energy of 30 g of this fluid?
If the fluid leaves a system at a flow rate of 5 g/min, at what rate does it
transport internal energy out of the system?
What would you need to know to calculate the specific enthalpy of this fluid?

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Exercise 3
Five hundred kilograms per hour of steam drives a turbine. The steam enters
the turbine at 44 atm and 450C at a linear velocity of 60 m/s and leaves at a
point 5 m below the turbine inlet at atmospheric pressure and a velocity of 360
m/s. The turbine delivers shaft work at a rate of 70 kW, and the heat loss from
the turbine is estimated to be 104 kcal/h. Calculate the specific enthalpy
change associated with the process.

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Energy balance: Reactive and

non reactive system

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Energy balance: Reactive system

Enthalpy of a reaction or energy change of a
reaction H, is the amount of energy or heat
absorbed in a reaction.
If the energy is required, H is (+), and if energy
is released, the H, is (-).

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Using Formulas to Calculate H

When standard enthalpies of formation, Hfo, for
all products and reactants are available, we
have
Hreaction = (Hfo products) - (Hfo reactants)

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Energy balance: Reactive system

Heat of Combustion
The quantity of heat released when a given
amount of a substance burns is called the heat
of combustion.
The amount of heat released when one mole of
that substance is burned is called the molar heat
of combustion.
These measurements are usually taken at
thermodynamic standard conditions (298 K and
1 atm), and it is symbolized by Hocomb.
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Heat of Combustion
Combustion is always exothermic, Hc is negative.
By definition, the heat of combustion is minus the
enthalpy change for the combustion reaction, i.e., -Hc.
By definition, the heat of combustion is a positive value.
Heat of Combustion can be measured experimentally.

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Heat of
Substance Combustion
(kJ/mol)

Combustion Reaction

Hreaction(kJ/
mol)

methane

890

CH4(g) + 2O2(g) ---> CO2(g) + 2H2O(l)

H = -890

ethane

1560

C2H6(g) + 7/2O2(g) ---> 2CO2(g) + 3H2O(l)

H = -1560

propane

2220

C3H8(g) + 5O2(g) ---> 3CO2(g) + 4H2O(l)

H = -2220

butane

2874

C4H10(g) + 13/2O2(g) ---> 4CO2(g) + 5H2O(l)

H = -2874

octane

5460

C8H18(g) + 25/2O2(g) ---> 8CO2(g) + 9H2O(l)

H = -5460

methanol

726

CH3OH(l) + 3/2O2(g) ---> CO2(g) + 2H2O(l)

H = -726

ethanol

1368

C2H5OH(l) + 3O2(g) ---> 2CO2(g) + 3H2O(l)

H = -1368

propan-1-ol

2021

C3H7OH(l) + 9/2O2(g) ---> 3CO2(g) + 4H2O(l)

H = -2021

butan-1-ol

2671

C4H9OH(l) + 6O2(g) ---> 4CO2(g) + 30

5H2O(l)

H = -2671

Energy balance: Reactive system

Heat of Formation, Hfo
is the heat evolved from the synthesis reaction
of one mole of the substance from the standard
state of its constituent elements.
The standard state of an element is defined as
pure, at 1 atm pressure, and in the phase it
would normally occur at 298K.
H = Hof (products) - Hof (reactants)
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Example
Calculate the heat given off when one mole
of B5H9 reacts with excess oxygen according
to the following reaction:
Compound

Hf (kJ/mol)

B5H9(g)

73.2

B2O3(g)

-1272.77

O2(g)

H2O(g)

-241.82
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Solution:

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