CN 2101: Material and Energy

Balances

Lecture 6: Steady State Energy Balances

Department of Chemical and Biomolecular Engineering

National University of Singapore

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RECAP FROM PREVIOUS SESSION

2.1 Basic principles of energy balances

2.1.1 Basic Forms of Energy (Review on Thermodynamics)
2.1.2 Energy Balance Equation
2.1.3 Energy Balance on Closed Systems
2.1.4 Energy Balance on Open Systems (Steady State)

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2.1.1 BASIC FORMS OF ENERGY

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2.1.2 GENERAL ENERGY BALANCE EQUATION

The law of thermodynamics state that energy

cannot be created nor destroyed!!

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2.1.3 ENERGY BALANCES ON CLOSED SYSTEMS

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2.1.3 ENERGY BALANCES ON CLOSED SYSTEMS

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2.1.4 ENERGY BALANCES ON OPEN SYSTEMS

For continuous systems:

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2.1.4 ENERGY BALANCES ON OPEN SYSTEMS

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2.1.4 ENERGY BALANCES ON OPEN SYSTEMS

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2.1.4 ENERGY BALANCES ON OPEN SYSTEMS

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2.1.4 ENERGY BALANCES ON OPEN SYSTEMS

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OVERVIEW FOR THIS SESSION

2.2 Heat Capacities and Enthalpy Changes

2.2.1 Reference State and State Properties
2.2.2 Methods of determining Enthalpies
– Tables
– Charts
– Equations
– Computerized Databases

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2.2.1 REFERENCE STATES AND
STATE PROPERTIES

• In thermodynamics, Pressure (P), Volume (V) and

Temperature (T) are measurable properties. They
can be measured through experimental means

� and Enthalpy (𝐻𝐻)

• Internal Energy (𝑈𝑈) � are conceptual
properties. They are NOT measurable and can only
be determined through measurable properties (e.g.
P, V, T)

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2.2.1 REFERENCE STATES AND
STATE PROPERTIES

• Extensive properties are properties that depend on

the size of the system (e.g. U, H, V, m, n)

• Intensive properties are properties that DO NOT

� 𝐻𝐻,
depend on the size of the system (e.g. 𝑈𝑈, � 𝑉𝑉,
� P, T)

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REFERENCE STATES

� and 𝐻𝐻
• Absolute values of 𝑈𝑈 � cannot be determined.
� and 𝐻𝐻
• The change of 𝑈𝑈 � (∆𝑈𝑈
� and ∆𝐻𝐻)
� can be
determined from PVT properties

� and 𝐻𝐻
• A convenient way to tabulate changes in 𝑈𝑈 � is
to choose a reference state based on PVT

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REFERENCE STATE AND ENTHALPY CHANGES
� = 𝐻𝐻
1. Choose a reference state ( e.g. 0℃, 1 atm, 𝐻𝐻 �𝑜𝑜 )

�
2. Measure the PVT and determine the enthalpy change ∆𝐻𝐻
from the reference state to the new conditions
� = 𝐻𝐻
∆𝐻𝐻 � − 𝐻𝐻
�𝑜𝑜

� cannot be determined absolutely, so we set the reference

3. 𝐻𝐻
�𝑜𝑜 @ the reference state to be zero
state 𝐻𝐻

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REFERENCE STATE AND ENTHALPY CHANGES

EXAMPLE

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REFERENCE STATE AND ENTHALPY CHANGES

EXAMPLE

In principle, various reference states can be adopted:

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2.2.2 METHODS OF DETERMINING
ENTHALPY

1. Enthalpy / Energy tables

2. Enthalpy / Energy charts
3. Heat capacities equations
4. Computerized databases

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1. ENTHALPY TABLES – STEAM TABLES

Recall: Phase Diagram (P-T data)

Where are the

subcooled
liquid, saturated
liquid/steam,
superheated
steam regions?

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STEAM TABLES
(SATURATED STEAM-TEMPERATURE TABLE)

REF: FELDER, ROUSSEAU & BULLARD (TABLE B.5)

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STEAM TABLES
(SATURATED STEAM-PRESSURE TABLE)

REF: FELDER, ROUSSEAU & BULLARD (TABLE B.6)

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STEAM TABLES
(SUPERHEATED STEAM)

REF: FELDER, ROUSSEAU & BULLARD (TABLE B.7)

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WORKED EXAMPLE 1

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WORKED EXAMPLE 1

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2. ENTHALPY / ENERGY CHARTS

Example P-H Chart (Pressure – Enthalpy chart) for n-butane

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WORKED EXAMPLE 2

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3. HEAT CAPACITY EQUATIONS
For batch process (closed system), assuming no work done, the
energy change will be:

∆𝑈𝑈 = 𝑄𝑄

Specific internal energy of a substance depends strongly on

temperature.

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3. HEAT CAPACITY EQUATIONS
By definition, the heat capacity at constant volume of a
substance, denoted by 𝐶𝐶𝑣𝑣 is

�
∆𝑈𝑈 �
𝜕𝜕𝑈𝑈
𝐶𝐶𝑣𝑣 𝑇𝑇 = lim =
∆𝑇𝑇→0 ∆𝑇𝑇 𝜕𝜕𝜕𝜕 𝑉𝑉
� for a rise in temperature from T to T+dT at
The change in 𝑈𝑈
constant volume will be:
� = 𝐶𝐶𝑉𝑉 𝑇𝑇 𝑑𝑑𝑑𝑑
𝑑𝑑 𝑈𝑈
And hence
𝑇𝑇2
� = 𝑈𝑈
∆𝑈𝑈 �2 − 𝑈𝑈
�1 = � 𝐶𝐶𝑉𝑉 𝑇𝑇 𝑑𝑑𝑑𝑑
𝑇𝑇1

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WORKED EXAMPLE 3
Calculate the heat required to raise 200kg of nitrous oxide (N2O) from 20℃ to
150℃ in a constant-volume vessel. The constant-volume heat capacity of N2O
in this temperature range is given by the equation:
𝑘𝑘𝑘𝑘
𝐶𝐶𝑣𝑣 = 0.855 + 9.42 × 10−4 𝑇𝑇
𝑘𝑘𝑘𝑘 � ℃
Where T is in ℃.

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3. HEAT CAPACITY EQUATIONS
Consider heating a substance at constant pressure and consider
the resulting change in enthalpy.
By definition, the heat capacity at constant pressure, 𝐶𝐶𝑝𝑝 𝑇𝑇 is:
∆𝐻𝐻� �
𝜕𝜕𝐻𝐻
𝐶𝐶𝑝𝑝 𝑇𝑇 = lim =
∆𝑇𝑇→0 ∆𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃
� for a rise in temperature from T to T+dT at
The change in 𝐻𝐻
constant pressure will be:
� = 𝐶𝐶𝑝𝑝 𝑇𝑇 𝑑𝑑𝑑𝑑
𝑑𝑑 𝐻𝐻
And hence
𝑇𝑇2
� = 𝐻𝐻
∆𝐻𝐻 �2 − 𝐻𝐻
�1 = � 𝐶𝐶𝑝𝑝 𝑇𝑇 𝑑𝑑𝑑𝑑
𝑇𝑇1

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3. HEAT CAPACITY EQUATIONS
For a process 𝐴𝐴 𝑇𝑇1 , 𝑃𝑃1 → 𝐴𝐴 𝑇𝑇2 , 𝑃𝑃2 , we can construct a 2-step
process path:
𝐴𝐴 𝑇𝑇1 , 𝑃𝑃1 → 𝐴𝐴 𝑇𝑇1 , 𝑃𝑃2 → 𝐴𝐴 𝑇𝑇2 , 𝑃𝑃2

�
To calculate ∆𝑈𝑈:

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3. HEAT CAPACITY EQUATIONS
For a process 𝐴𝐴 𝑇𝑇1 , 𝑃𝑃1 → 𝐴𝐴 𝑇𝑇2 , 𝑃𝑃2 , we can construct a 2-step
process path:
𝐴𝐴 𝑇𝑇1 , 𝑃𝑃1 → 𝐴𝐴 𝑇𝑇1 , 𝑃𝑃2 → 𝐴𝐴 𝑇𝑇2 , 𝑃𝑃2

�
To calculate ∆𝐻𝐻:

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3. HEAT CAPACITY EQUATIONS

Heat capacities 𝐶𝐶𝑣𝑣 and 𝐶𝐶𝑝𝑝 are physical properties of

materials and are tabulated in standard references e.g.
Perry’s Chemical Engineers Handbook and Felder’s
textbook Table B.2 (next slide).

Units expressed in energy per unit species amount

(mass or moles) per unit temperature interval

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3. HEAT CAPACITY EQUATIONS

For ideal gases:

𝐶𝐶𝑝𝑝 = 𝐶𝐶𝑣𝑣 + 𝑅𝑅

For liquids and solids (incompressible):

𝐶𝐶𝑝𝑝 ≈ 𝐶𝐶𝑣𝑣

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3. HEAT CAPACITY EQUATIONS

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WORKED EXAMPLE 4
15 kmol/min of air is cooled from 430℃ to 100 ℃. Calculate the
required heat removal rate using the heat capacity equation,
assuming negligible change in 𝐸𝐸𝑘𝑘 and 𝐸𝐸𝑝𝑝 .

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USING HEAT CAPACITIES
EQUATIONS

• The equations in Table B.2 applies to 1atm pressure,

or non-isobaric processes of gases at ideal or nearly
ideal gas state (i.e. low P and high T)

• For enthalpy changes at pressures high enough (or

temperature low enough) for the gases to be far
from ideal, enthalpy tables or more accurate heat
capacity formulas should be used

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ESTIMATION FOR MIXTURES
RULE 1:
For a mixture of gases or liquids, calculate the total enthalpy
change as the sum of the enthalpy change for the pure mixture
components (neglecting enthalpy changes for mixing, which is
good approximation for gas mixtures and mixtures of similar
liquids)

RULE 2:
For highly dilute solutions of solids or gases in liquids, neglect
the enthalpy change of the solute (the more dilute the solution,
the better the approximation)

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ESTIMATION FOR MIXTURES

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4. USING COMPUTERIZED DATABASES
– E.G. HYSYS

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 End of Lecture 6
Steady-state ENERGY Balances
Dr Cindy Lee

Department of Chemical and Biomolecular Engineering

National University of Singapore
NUS Faculty of Engineering, Block E4, Unit #05-12
+65 6601 3877 (Tel) chellyc@nus.edu.sg
https://blog.nus.edu.sg/chellyc

ACKNOWLEDGEMENT: CN2101 AY2019/2020 Lecture notes (Prof. Lanry Yung)

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