Energy balances – Introduction Felder (7.

0)

1 Energy balances
1.1 Introduction Felder (7.0)
1.1.1 Background
As for mass balances, the conservation laws extend in an analogous way for energy. This
chapter will cover basic introductory concepts and then energy balances over non-reacting
systems as well as over reacting systems.

Before being able to calculate an energy balance it is important to understand the terms needed
for such [Move to chapter 1?]. These include terms which may already be familiar to you. For
a full list of terms as well as shorter definitions, see the Glossary.

Intensive vs extensive properties

Video 1.1: Intensive vs extensive properties (YouTube)

Steady state vs unsteady (transient) state

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Video 1.2: Steady state (YouTube)

Systems and boundaries

System: Defined space to which calculations will be applied
Boundary: The border separating the system and everything else
Surroundings: The part outside the system
Open system: Defined space over which matter and energy can flow
Closed system: Defined space over which only energy can flow
Isolated system: Defined space over which neither matter nor energy can flow

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Video 1.3: Systems: Open, closed and isolated systems (YouTube)

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 Energy balances – Introduction Felder (7.0)

State vs path functions

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Video 1.4: State vs path functions (YouTube)

Iso-

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Video 1.5: Iso- (isothermal, isochoric, isobaric, …) (YouTube)

1.1.2 Heat
Heat (Q, in units of kJ, kJ/s, kW or kJ/kg) is the disorganized transfer of energy that results due
to a temperature gradient. Heat is not included in the energy of a system but rather as the
transfer of energy across the system boundary. Heat (transfer) can be through conduction (no
movement of fluids), convection (movement of fluids) or radiation (no temperature gradient
needed). More information on this is given in a separate chapter.

Relating heat to energy balances and thermodynamics, for a closedm system heat, energy and
work are related by:

DE = Q + W 1.1

Where:
E = Energy
Q = Heat, and
W = Work

And DE = Ef – E0, is the change in energy from the initial to final states, inside the system.

1.1.3 Work
Work is typically the transfer of energy through movement due to a force. It is typically broken
down into the following subcategories:

- Expansion work (W∆" ) [mechanical work], also called PV Work (WPV), is the work needed to
change a systems volume.
- Flow work (WFlow) is the work performed when a stream exits or enters a system.
- Shaft work (WS) is the work due to mechanical work changing the pressure, e.g. from pumps
compressors, turbines etc.
- Electrochemical work (Wel) is the work performed due to such things as batteries or fuel cells.
- Other forms of work (Wother) might include electromagnetic work, sound work, etc.

Adding these gives us the total work of the system:

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 Energy balances – Introduction Felder (7.0)

W = W!"#$ + W∆& + W' + W(" + W#)*(+ 1.2

This is typically re-written as:

W = W!"#$ + W, 1.3

Where:
Wn is all the non-flow work

Example 1.1: Example 5.1 Himmelblau (old version)

Solution:

Lost work Reversibility (Elliott and Lira p42)

1.1.4 Energy
Energy is often referred to as the “ability to perform work”. However, the definition needs to
further extend to include the concept of being able to release heat. Therefore, the definition of
energy can be said to be either the ability to perform work or to release heat.

As with work, energy can have various forms:

- Kinetic energy (EK) is the energy due to movement of the centre of mass of an object.
- Rotational energy (ER) is the energy when the centre of mass is at rest but there is rotation.
- Potential energy (EP) is the energy due to an elevated height relative to a reference point.
- Electric energy (Eel) is energy stored in such things as a capacitor.
- Surface energy (ES) is the intermolecular energy creating a surface.
- Internal energy (U) is the energy of molecules. It can be seen as the sum of thermal energy,
chemical bonding energy and latent energy on a molecular level.

Adding these gives us the total energy of the system:

E = U + E- + E. + E/ + E(" + E0 + E#)*(+ 1.4

For the sake of this course, we will only be looking at kinetic energy (EK), potential energy
(EP) and internal energy (U).

Himmelblau 9.2.5 - 9.2.8

1.1.5 Internal Energy

For a closed system it was shown that:
DE = Q + W 1.1

Since energy was defined as:

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 Energy balances – Introduction Felder (7.0)

E = U + E- + E. + E/ + E(" + E0 + E#)*(+ 1.5

For a system with no potential, kinetic, rotational etc. energy, i.e. no movement or energy due
to height or other external factors, this can be simplified to:

E=U 1.6

Therefore:
DU = Q + W 1.7

Strictly speaking, this should be written as:

dU = δQ + δW 1.8

where the internal energy term is an ordinary differential, while Q and W are partial
differentials.

For a constant volume (closed) system, where all W terms are also zero, we can simplify this
as:
dU = δQ 1.9
Or
DU = Q 1.10

Example 1.2:

Solution:

1.1.6 Enthalpy
NEED TO INCLUDE CP DEFINITION IN HIMMELBLAU (5.xxx)
Enthalpy is defined as:

H = U + PV 1.11

where:
H: Enthalpy (J)
U: Internal Energy (J)
P: System pressure (N/m2)
V: System volume (m3)

Since internal energy is a function of temperature, enthalpy too is a function of temperature.

For process purposes, it is common to work with enthalpy.

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 Energy balances – Introduction Felder (7.0)

Enthalpy is measured according to some known value. This is known as the basis. Typically,
the basis is chosen as elements in their standard state (at 1 atm and 298.15K) à H = 0.

Since basis is elements, we define the heat of formation as the following:

H!1 : Standard enthalpy of formation
0: standard state
f: formation

We can only add enthalpies which have the SAME basis.

Example 1.3: Stream enthalpy at standard conditions

Given a stream of CO(g), flowing at 100 mol/min at a temperature of 298.15 K and pressure of 1 bar, calculate
the enthalpy.

Given: 𝐻!" CO(g) = -110.53 kJ/mol

Solution:
Basis: Elements in standard state at 298.15K and 1 bar

Enthalpy flow:
𝑚𝑜𝑙 𝑘𝐽
𝐻̇ = 100 × (−110.53)
𝑚𝑖𝑛 𝑚𝑜𝑙
𝑘𝐽
𝐻̇ = −11 053
𝑚𝑖𝑛

Converting:
𝑘𝐽 1000 𝐽 1𝑚𝑖𝑛
𝐻̇ = −11. 053 × 10# × × = −1.84 × 10$ 𝐽/𝑠
𝑚𝑖𝑛 𝑘𝐽 60𝑠
𝐻̇ = −1.84 𝑥 10$ 𝑊 = −184 𝑘𝑊

The negative value indicates that energy is being released, i.e. exothermic

Q: Is the basis always 25°C and 1 atm?

A: No. It is the basis when we are dealing with reactions. Most data is given at standard
conditions and, particularly enthalpies of formation (H0f) is needed.

In addition to 25°Cand 1atm basis entails elements in standard state having H0f = 0 kJ/mol (this
accounts for formation and breaking of bonds in a reactor).

It is possible to measure these properties under other conditions for use as a basis. However,
25°C and 1 atm is the most convenient for measurement.

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 Energy balances – Introduction Felder (7.0)

Video 1.6: Energy balance – Introduction (YouTube)

1.1.7 Specific Heat

Specific heat (at constant pressure): C.! , J.K-1.mol-1 OR J.K-1.kg-1

Definition:
"#
C.! = / 0 "$ %&,(
1.12

Where:
𝑥2 = composition
P = Pressure
i.e., constant composition and pressure

Enthalpy under standard conditions:

Ḣ = ṅ H)* 1.13

Calculation of enthalpy under non-standard conditions:

$%
Ḣ = ṅ H)* + ṅ 5 C.! dt
$&

Where:
T1 = reference temperature (K)
T2 = new temperature (K)

$% $% "#
∫$& C.! dt = ∫$& / "$ 0 dt = H|$% − H|$& 1.14
%&,(
i.e., if we don’t have Cp data, we can use the enthalpy data (if available)

NOTE:
If Cp is constant, i.e., NOT dependent on T, then:
$%
$%
5 C.! dt = C.! T;$ = C.! (T+ − T, ) = C.! ∆T
$& &

If Cp is a function of temperature the integral becomes more complex and integral tables may
be needed.
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 Energy balances – Introduction Felder (7.0)

Example 1.4: Stream enthalpy at standard conditions

Given a stream of CO(g), flowing at 100 mol/min at a temperature of 350 K and pressure of 1 bar, calculate
the enthalpy.

Given: Cp = 29.14 J/K.mol

Solution:
∴ 𝐻̇ = −11.053 × 10! 𝑘𝐽. 𝑚𝑖𝑛"# + 𝑛̇ 𝐶4$ ∆𝑇
𝐻̇ = −11.053 × 10! 𝑘𝐽. 𝑚𝑖𝑛"# + [100𝑚𝑜𝑙. 𝑚𝑖𝑛"# × 29.14𝐽. 𝐾 "# 𝑚𝑜𝑙"# × (350 − 298.15)𝐾]
𝐻̇ = −11.053 × 10! 𝑘𝐽. 𝑚𝑖𝑛"# + 151 090.9𝐽. 𝑚𝑖𝑛"#
𝐻̇ = −11.053 × 10! 𝑘𝐽. 𝑚𝑖𝑛"# + 151.0909𝑘𝐽. 𝑚𝑖𝑛"#
𝐻̇ = −10.902 × 10! 𝑘𝐽. 𝑚𝑖𝑛"#

NOTE:
From previous examples, we see that H = -11.053 x 103 kJ/min when T = 298.15K, and when
T = 350 K, H = -10.902 x 103 kJ/min. Therefore, energy is taken in when the reaction proceeds
at a higher temperature of 350K
(More negative to less negative à energy taken in)

Logically, to move from -10°C to -5°C, energy is taken in as we are heating the substances.
Therefore, a change from a negative larger magnitude value to a negative smaller magnitude
value, energy is absorbed or taken in.

Constant composition (x2):

- No phase changes
- No reaction
- No mixing

Note:
- We cannot measure specific heat directly; we measure enthalpy relative to some basis.
- In practice, enthalpies are measured, and a polynomial model is fitted to the data in order to
obtain specific heat. The model has different constants depending on which units of
temperature, say, were used to make the enthalpy measurements

Cp vs Cv

1.1.8 Entropy (S) (not part of CHMT2023A)

1.1.9 Gibb’s Free Energy (G) (not part of CHMT2023A)
1.1.10 Helmholtz Energy (A) (not part of CHMT2023A)

1.1.11 Thermodynamics
- Zeroth Law
- First Law of Thermodynamics
- Second Law of Thermodynamics
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 Energy balances – Steam Tables

- Third Law of Thermodynamics

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Video 1.7: Thermodynamic laws (YouTube)

1.2 Steam Tables

1.2.1 Introduction
Steam tables (for example Rogers and Mayhew, 1995) are a collection of data for, amongst
others, the enthalpy of steam related to its state, temperature, and pressure. These are collated
into single sets of data and used to calculate the data of liquid systems in various scenarios e.g.,
energy balances.

The data is often compiled into three main parts for water (steam):
- Saturated Water and Steam;
- Superheated and Supercritical Steam; and
- Further Properties of Water and Steam

While colloquially called steam tables, most compilations also include a section on the
properties of other materials such as Mercury, Ammonia and CFCs.

Felder 7.5

1.2.2 Saturated Water and Steam

This collection of data includes the enthalpy and entropy of liquid and gaseous water for
saturated water at varying temperatures or pressures. The data includes the internal energy,
specific volume as well as the corresponding vaporisation data as appropriate.

1.2.3 Superheated and Supercritical Steam

The specific volume, internal energy, enthalpy and entropy are given for water vapour that is
hotter than its saturation limit, i.e. superheated steam. Data is also given for water under
supercritical conditions.

1.2.4 Further Properties of Water and Steam

The steam tables may also give data such as the specific volume of the liquid phase, specific
heat, thermal conductivities, and Prandtl Numbers (Pr). Certain tables also include data on
compressed water and/or ice.

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 Energy balances – Steam Tables

Video 1.8: Energy balance – Steam tables (Part 1) (YouTube)

1.2.5 Other Properties

Like above, it is also possible to obtain enthalpy and entropy data for Mercury, Ammonia, and
other CFCs. While not strictly speaking water, the steam table compilations sometimes also
give the specific heat values for air and specific gases, enthalpies and entropies, heats of
reaction, partial pressure, and equilibrium data as well as conversion factors and general
information.

Video 1.9: Energy balance – Steam tables (Part 2) (YouTube)

Example 1.5: Using steam tables (I)

Using the ‘Steam Tables’, find:

(a) The enthalpy of saturated water at 20 bar and Ts.
(b) The enthalpy of saturated steam at 90 bar and Ts.
(c) The specific volume of saturated steam at 30 bar and Ts.
(d) The specific volume of saturated water at 25°C and Ps.
(e) The enthalpy of steam at 10 bar and 300°C.
(f) The internal energy of saturated steam at 0.525 bar and Ts.
(g) Heat of vaporisation at 201 bar and Ts.
(h) Enthalpy of steam at 200°C and 5 bar.
(i) The enthalpy of superheated steam at 350°C and 85 bar

Solution:
(a) 909 kJ/kg
(b) 2743 kJ/kg
(c) 0.06665 m3/kg
(d) 0.0010030 m3/kg
(e) 3052 kJ/kg
(f) 2563 kJ/kg
(g) 572 kJ/kg

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 Energy balances – Steam Tables

(h) 2857 kJ/kg

(i) 2974.5 kJ/kg

Example 1.6: Using steam tables (II)

We have saturated steam at 10 bar with 𝑉= = 0.02m3/kg. How much liquid and vapor do we have?

Solution:
For saturated steam:
P = 10 bar; Ts = 179.9°C; 𝑉=' = 0.1944 m3/kg
But the specific volume of the system is only 0.02 m3/kg. Therefore, the system is not only steam; there must
be some liquid present in equilibrium with the steam.

For liquid water:

P = 10 bar à
P = 7.920 bar and 𝑉=( = 0.1114 × 10-2 m3/kg
P = 10.03 bar and and 𝑉=( = 0.1128 × 10-2 m3/kg

By interpolation:
(0.1128 × 10)* − 0.1114 × 10)* )𝑚# E𝑉=( − 0.01114 × 10)* F𝑚#
𝑘𝑔 𝑘𝑔
=
(10.03 − 7.920)𝑏𝑎𝑟 (10 − 7.920)𝑏𝑎𝑟
(0.1128 × 10)* − 0.1114 × 10)* )𝑚# /𝑘𝑔 × (10 − 7.920)
𝑉=( = + 0.01114 × 10)* 𝑚# /𝑘𝑔
(10.03 − 7.920)
𝑉=( = 1.125 × 10)* 𝑚# /𝑘𝑔

Total Mass Balance: Mt = Ml + Mg [1]

Total Volume balance: Vt = Vl + Vg [2]
Since we only have specific volumes, (2) becomes:
Mt𝑉=t = Ml𝑉=l + Mg𝑉=g [3]

Assuming 1 kg of steam:
𝑀+ 𝑉I+ = 𝑀( 𝑉I( + (𝑀+ − 𝑀( ) 𝑉I'
𝑀+ 𝑉I+ = 𝑀( 𝑉I( + 𝑀+ 𝑉I' − 𝑀( 𝑉I'
𝑀( E𝑉I( − 𝑉I' F = 𝑀+ E𝑉I+ − 𝑉I' F
Steam quality derivation
(0.02 − 0.1944)𝑚# /𝑘𝑔
𝑀( = 1𝑘𝑔
(1.125 × 10)# − 0.1944)𝑚# /𝑘𝑔
𝑀( = 0.9024𝑘𝑔

Therefore:
Mg = (1 – 0.9024) kg AND Mg = 0.0976 kg

Example 1.7: Using interpolation in steam tables

Find the enthalpy of steam at T = 175°C and P = 5 bar. Interpolate between saturation point and 200°C.

Solution:
At saturation: T = 151.8°C; P = 5 bar; hg = 2749 kJ/kg
And at T = 200°C and P = 5 bar: hg = 2857 kJ/kg

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 Energy balances – Steam Tables

Therefore:
2857 − 2749
ℎ' = K L . (175 − 151.8) + 2749
200 − 151.8
hg = 2801 kJ/kg

Steam quality
The quality of steam is defined as the mass fraction (or percentage) of vapour in the mixture.

-
x = -, 1.15
-

Since the volume is constant:

V = V. + V/ 1.16

And, by definition:
V = mVA 1.17

We can re-write the volume as:

A m$ = V
V A. m. + V
A/ m/ 1.18

Divide by mT:
1 --
0 1 . -.
0 1 , -,
0
--
= --
+ --
1.19
1 1
A = 0. - . + 0, - ,
V 1.20
- - - -

From the definition of quality:

-
x = -, 1.15
-

We obtain:
-- - -
--
− x = -- − -, 1.21
- -
-- 3 -,
1−x= --
1.22
-
1 − x = -. 1.23
-

Substituting 1 and 9 into 6:

A = (1 − x). V
V A. + x. V
A/ 10

And re-arranging:
A=V
V A. − x. V
A. + x. V
A/ 11
A−V
V A. = x. DVA/ − VA. E 12
01 301.
x= 1 , 30
0 1.
13

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 Energy balances – General Energy Balance Equation

1.2.6 H-T-S-P type diagrams/Mollier Diagrams

Instead of a tabulated form of the steam tables, an alternative is a graphical representation.

[4 x diagrams here]

Example 1.8:

Solution:

Video 1.10: Energy balance – Mollier diagrams (YouTube)

1.3 General Energy Balance Equation

1.3.1 General derivation energy balance
From the conservation laws we know that In = Out (during steady state)

In Out

When considering energy this can be in the form of energy due to material flowing through the
system, work or added heat.

Min Mou
t

Q
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 Energy balances – General Energy Balance Equation

where:
M = Mass (kg or kg/s)
W = Work (J or J/s)
Q = Heat (J or J/s)

Energy balance becomes:

In = Out 1.24
Energy45 = Energy678 1.25
Energy from flow45 + Q̇ + Ẇ = Energy from flow678 1.26

Rearranging:
0 = Energy from flow45 − Energy from flow678 + Q̇ + Ẇ 1.27

But this is only true for steady state – if not at steady state:
(Change in Energy) = (Energy from flow45 − Energy from flow678 ) + Q̇ + Ẇ 1.28

Energy is going to be defined as the internal energy (U) of the system/flow terms:
9:
98
= (U45 − U678 ) + Q̇ + Ẇ 1.29

From the definition of enthalpy:

H = U + PV (link to other definition)

Since U is not possible to measure, we wish to replace with enthalpy, therefore:

U = H − PV 1.30

9:
98
= ((H − PV)45 − (H − PV)678 ) + Q̇ + Ẇ 1.31

Rearranging:
9:
98
= (H45 − H678 ) + Q̇ + Ẇ + Ẇ(0 1.32
9:
98
= ∑54;, H4 + Q̇ + Ẇ + Ẇ(0 1.33

What about kinetic and potential energy? These are forms of energy due to movement (flow
terms) or change with time (‘/dt’ terms).

9<:= >/ = >0 ?

98
= ∑54;,DH4 + E@ + E! E + Q̇ + Ẇ + Ẇ(0 1.34

Or:
1%
9A:= BC = DEF
% H%
98
= ∑54;, Ṁ G /H
A+
+
+ φ0 + Q̇ + Ẇ + Ẇ(0 1.35
4

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 Energy balances – General Energy Balance Equation

Typically, the kinetic and potential energy terms are ignored as they do not influence
temperature and work terms are written as a single term, so:
9:
= ∑54;,DMH A E + Q̇ + Ẇ + Ẇ(0 1.36
98 4

Or as a molar basis:
9:
= ∑54;, /NH0 + Q̇ + Ẇ + Ẇ(0 1.37
98 − 4

1.3.2 Specific energy balance examples

Some common forms of the energy balance:

Closed system, non-steady state

9:
98
= Q̇ + Ẇ + Ẇ(0 1.38

Closed system, Steady state

0 = Q̇ + Ẇ + Ẇ(0 1.39

Open system, Steady state

0 = ∑54;,DMHA E + Q̇ + Ẇ + Ẇ(0 1.40
4

Adiabatic process
9:
= ∑54;,DMHA E + Ẇ + Ẇ(0 1.41
98 4

Sign Conventions
[Q]: What does positive or negative Q represent?

Energy Balance/Enthalpy calculations

[A]: Positive Q is heat ADDED to a system. Negative Q is REMOVED from the system.

Heat Transfer
[A]: Positive Q is heat transferred from hot to cold, i.e., out of the system.

Therefore, definition of heat transfer is opposite in Energy Balance calculations to Heat Transfer
calculations.

BEWARE: When looking at both types of approaches in a single problem ensure the correct sign for Q.

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 Energy balances – Energy Balances for Non-Reacting Systems

Video 1.11: Energy balance – General equation (YouTube)

1.4 Energy Balances for Non-Reacting Systems

1.4.1 Introduction
Enthalpy vs. heat vs. latent heat

Example 1.9:

Using Simpson’s Rule, determine the enthalpy from 20°C to 200°C given the data below.

T [°C] 20 50 80 110 140 170 200 230

Cp [J/mol.°C] 28.95 29.13 29.30 29.48 29.65 29.82 29.99 30.1

Solution:
Note:
h = constant value of 30
7 points à 6 intervals (even number)
Therefore, we can use Simpson’s

Now:
*""
𝐻= $ 𝐶𝑝(𝑥)
*"

5 2
Simpson’s Rule: ∫6 𝑓(𝑥) ≈ [𝑓(𝑥3 ) + 4𝑓(𝑥* ) + 2𝑓(𝑥# ) + ⋯ + 2𝑓(𝑥4)* ) + 4. 𝑓(𝑥4)3 ) + 𝑓(𝑥4 )]
#

Therefore:
*""
ℎ
𝐻= $ 𝐶𝑝(𝑥) ≈ [𝐶𝑝3 + 4𝐶𝑝* + 2𝐶𝑝# + 4𝐶𝑝7 + 2𝐶𝑝$ + 4𝐶𝑝8 + 𝐶𝑝9 ]
*" 3
𝐻 ≈ 5305.6𝐽/𝑚𝑜𝑙

NOTE:
If we were asked to find the integral up to 230°C, this would have been an odd number of intervals and
Simpson’s would not work. Therefore, would need to use Simpson’s as above AND then add the last portion
by another technique, e.g., Trapezoidal Rule.

*#" *"" *#"

𝐻= $ 𝐶𝑝(𝑥) ≈ >$ 𝐶𝑝(𝑥)? + >$ 𝐶𝑝(𝑥)?
*" *" :;<=>?4! >@A(B *"" CD6=BE?;F6( @A(B
ℎ
𝐻 ≈ 5305.6 + [𝐶𝑝9 + 𝐶𝑝H ] CD6=BE?;F6( @A(B
2
𝐻 ≈ 5305.6 + 902
𝐻 ≈ 6207𝐽/𝑚𝑜𝑙
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 Energy balances – Energy Balances for Non-Reacting Systems

Example 1.10:

Solution:

1.4.2 Heat of Formation

The heat of formation (also called the enthalpy of formation) is the energy (enthalpy) needed
to form one mole of a compound from its elements in their standard states.

Example 1.11:

Solution:

1.4.3 Heat of Mixing

The heat of mixing (also called the enthalpy of mixing) is the energy (heat) taken up or released
when two non-reacting materials mix. The heat of mixing is the energy needed to bring the
mixed substances back to their standard states (from changed temperature to original
temperature).

Video 1.12: Energy balance – Heat of mixing (YouTube)

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 Energy balances – Energy Balances for Non-Reacting Systems

Example 1.12:

Solution:

The Flory-Huggins solution theory is an approximation of the heats of mixing.

Add FH approximation

1.4.4 Heat of Vaporisation

The heat of vaporisation (also called the enthalpy of vaporisation or the heat of evaporation) is
the energy needed to convert a material from a liquid to a vapour.

Example 1.13:

Solution:

1.4.5 Heat of Fusion

The heat of fusion (also called the enthalpy of fusion) is the heat needed to change a material
from a solid to a liquid.

Example 1.14:

Solution:

The Joback method (often named Joback/Reid method) predicts eleven important and
commonly used pure component thermodynamic properties from molecular structure only.
[expand on this]

1.4.6 Heat of Sublimation

The heat of sublimation (also called the enthalpy of sublimation) is the heat required to sublime
one mole of a substance.

Example 1.15:

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 Energy balances – Energy Balances for Non-Reacting Systems

Solution:

1.4.7 Heat of Melting

Example 1.16:

Solution:

1.4.8 Evaporation vs. Boiling

From the Clausius-Clapeyron equation it can be shown that the boiling point of water can be
calculated by:

3,
Rln(PJ ) 1
TI = Y + [
∆HHK! TJ

where:
TB = the normal boiling point, K
R = the ideal gas constant, 8.314 J/K.mol
P0 = the vapor pressure at a given temperature, atm
DHvap = the heat of vaporization of the liquid, J/mol
T0 = the given temperature, K

https://youtu.be/vRS4jdgYjPs
Video 1.13: Evaporation vs boiling (YouTube)

Example 1.17:

Solution:

1.4.9 Phase Diagrams

Example 1.18:

Solution:

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 Energy balances – Energy Balances for Reacting Systems

1.5 Energy Balances for Reacting Systems

1.5.1 Introduction

1.5.2 Heat of Reaction

The heat of reaction (also called the enthalpy of reaction) is the energy involved in converting
various chemicals via chemical reaction, into another.

Video 1.14: Energy balance – Heat of reaction (YouTube)

Example 1.19:

Solution:

1.5.3 Heat of Combustion

The heat of combustion for a fuel, coal or oil, is known as the heating value of the fuel. A
Lower (Nett) Heating Value (LHV) and a Higher (Gross) Heating Value (HHV) are both
defined, based on whether the water in the combustion products is in the form of a vapour
(LHV) or a liquid (HHV).

The HHV can be determined within 3% using the Dulong1 formula:

O
HHV (BTU/lb) = 14.544C + 62.028. dH − e + 4050S
8

Where C, H, O and S are the weight fractions of Carbon, Hydrogen, Oxygen and Sulphur
respectively. These are typically obtained from flue gas analyses.

Example 1.20:

Solution:

1
Lowry, HH (ed), 1945. Chemistry of Coal Utilization, Ch. 4, Wiley: New York
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 Energy balances – Non-Steady State Energy Balances

1.6 Non-Steady State Energy Balances

Example 1.21:

Solution:

1.6.1 Combined Mass and Energy Balances

Example 1.22:

Solution:

1.7 Additional Concepts

1.7.1 Isenthalpic, isentropic, adiabatic, isobaric, adiabatic flame temperature, vapour
pressure

1.8 Non-Flow Processes

1.8.1 Joule-Thomson Expansion

Video 1.15: Energy balance – Joule Thomson expansion (YouTube)

1.8.2 Reversible processes

1.8.3 Efficiency

1.9 Flow Processes

1.9.1 Refrigeration
1.9.2 Carnot Cycle
1.9.3 Other Cycles

1.10 Enthalpy departures

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 Energy balances – Psychometry

1.11 Psychometry

1.12 Pressure changes vs. altitude:

Atmospheric pressure changes with altitude by the following equation:

LB
Lh MN gMh
P = PJ d1 − e ≈ PJ . exp d− e
TJ RTJ

where:
P = Atmospheric pressure (Pa)
P0 = Sea level standard atmospheric pressure (101 325 Pa)
L = Temperature lapse rate (0.0065 K/m)
h = height above sea level (m)
T0 = sea level standard temperature (298.15K)
g = Standard gravity (9.80665 m/s2)
M = molar mass of dry air (0.0289644 kg/mol)
R = universal gas constant (8.31447 J/mol.K)

Therefore:
(P.RJSST).(J.J+RPSVV)
0.0052h (R.W,VVX).(J.JJST) (9.80665). (0.0289644). h
P = 101325 d1 − e ≈ PJ . exp Y− [
298.15 (8.31447). (298.15)

P = 101325(1 − 0.000017441h)T.+TTXX ≈ 101325. exp(−0.00011458. h)

P = (101325 − 1.767198h)T.+TTXX ≈ 101325. exp(−0.00011458. h)

Additional Reading
Balmer, RT, 2011. Modern Engineering Thermodynamics, Academic Press.
Elliott, JR, Lira, CT, 2012. Introductory Chemical Engineering Thermodynamics, 2nd ed.,
Pearson International Edition.
Felder RM, Rousseau RW, 2000. Elementary Principles of Chemical Processes, 3rd ed., Wiley.
Himmelblau, DM, 2012. Basic Principles and Calculations in Chemical Engineering, 8th ed.,
Prentice-Hall International.
Koretsky, MD, 2013. Engineering and Chemical thermodynamics, 2nd ed., Wiley.
Reklaitis, GV, 1983. Introduction to Material and Energy Balances, Wiley.
Rogers, G, Mayhew, Y, 1992. Engineering Thermodynamics – Work and Heat Transfer, 4th
ed., Pearson – Prentice Hall.
Rogers, G, Mayhew, Y, 1995. Thermodynamic and Transport Properties of Fluids (SI Units),
5th ed., Blackwell Publishing.
Sandler, SI, 2006. Chemical, biochemical, and Engineering Thermodynamics, 4th ed., Wiley.

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 Energy balances – Additional Reading

Skogestad, S, 2009. Chemical and Energy Process Engineering, CRC Press, Taylor & Francis
Group.

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 Energy balances – Problems

Problems
$
Example 1.23: Understanding energy - No work done on or by the system b) 𝐸'! ()* = 𝐸'+ ,)(()- = 𝑣,)(()- #
$

Explain your understanding of energy: Calculating potential energy: 𝐸! = 𝑚𝑔𝑧

𝐸'! = 𝑔𝑧 𝑣,)(()- = A2 × 2058 𝑚# 𝑠 "# = 64.76 𝑚𝑠 "$
a) What is energy (giving examples)? What are the different units of energy?
b) What is power? How does it differ from energy? c) It is significantly smaller than the calculated velocity.
Height equals vertical distance from reference to bottom of piston, plus half the
c) What is the difference between energy and heat? hight of the gas: d) The remaining energy is lost to other forms, mainly evaporation
d) List as many types of energy as possible. 𝐸'! = 9.81 𝑚𝑠 "# × (2 + 0.5(0.1))𝑚 e) Kinetic energy is converted to internal energy
e) For each answer listed above, give an example where it would be important to 𝐸'! = 20.11𝑘𝑔. 𝑚# . 𝑠 "# . 𝑘𝑔"$ = 20.11 𝑁. 𝑚. 𝑘𝑔"$ = 20.11 𝐽. 𝑘𝑔"$
understand this energy. From an energy balance that includes kinetic and potential energy:
0
c) 𝐸'! = 𝑔ℎ F + 𝐸'. + 𝐸'* G
𝑑D𝑈
= ID𝐻F/ + 𝐸'. + 𝐸'* G + 𝑄 + 𝑊
Solution: 𝑑𝑡
/1$
a) Energy is the ability to perform work or release heat. Energy is a conserved Height equals vertical distance from reference to bottom of piston, plus half the
quantity. The S.I. unit for energy is the joule (J), whose equivalent unit is the hight of the gas
If we assume no heat is leaving the water (all to temperature change), and for a closed
Newton Meter (Nm = kgm2s-2). Other units of energy include: the calorie (cal), 𝐸'! = 9.81 𝑚𝑠 "# × (0 + 0.5(0.1))𝑚 = 𝐸'! = 0.49 𝐽. 𝑘𝑔"$
system (water fixed volume of water falling), with no work, this becomes:
British thermal unit (Btu) and the foot-pound (ft lbf). F + 𝐸'. + 𝐸'* G
𝑑D𝑈
b) Power is the rate at which work is performed. It is a measure of the amount of d) 𝐸'! = 𝑔ℎ = 0
𝑑𝑡
energy consumed or transmitted per unit time.
c) Heat is the disorganized transfer of energy that results when systems of different Height equals vertical distance from reference to bottom of piston, plus half the This can be simplified to:
temperatures are contacted. In contrast to heat, work is organised energy transfer hight of the gas, which is half of the original height F + 𝐸'. + 𝐸'*G = 0
∆D𝑈
between systems. Heat is the energy transfer between systems, whereas energy is %.$
𝐸'! = 9.81 𝑚𝑠 "# × :0 + 0.5( ); 𝑚 = 𝐸'! = 0.24 𝐽. 𝑘𝑔"$
# F + 𝐸'. + 𝐸'*G − D𝑈
D𝑈 F + 𝐸'. + 𝐸'* G = 0
measured within the system boundary. ()* ,)(()-
d) Kinetic energy (Ek), rotational energy (ER), potential energy (Ep), electric energy F + 𝐸'* G − D𝑈
D𝑈 F + 𝐸'. G = 0
*Compressing the piston will also increase the internal energy of the system, ()* ,)(()-
(Eel), surface energy (Es), internal energy (U), solar energy.
which we have ignored here.
e) Rearranging:
• Kinetic energy: wind turbines ∆𝑈,)(()-→()* = 𝐸'* ()* − 𝐸'. ,)(()-
e) Energy is typically a difference and not an absolute value. The values above are
• Potential energy: hydro-electric power generation
relative to the reference. If a different reference point was chosen, the values 𝐶3 . ∆𝑇 = 𝐸'* ()* − 𝐸'. ,)(()-
• Internal energy: energy balance in chemical processing plant, nuclear energy 1 # 1
above would have been different. However, the differences in the values above
generation 𝐸'* ()* − 𝐸'. ,)(()- 𝑔ℎ()* − 2 𝑣 ,)(()- 9.81.210()* − 10#
would have been the same, even if the reference point was different. [See how this 2 ,)(()-
∆𝑇 = = = = 0.48 ℃
• Electric energy: electricity generation works for other forms of energy later in the section.] 𝐶3 𝐶3 4180
• Rotational energy: turbines Therefore, the temperature at the bottom is 25.48°C
• Solar energy: solar panels for energy generation f) A reference is a vertical height above the ground. In the calculations, we used the
term ‘z’, and not ‘h’ to calculate potential energy. ‘h’ is the distance from the f) Since energy is required for evaporation, it would cool the water.
ground, while ‘z’ is the distance from the reference point.
Example 1.24: Potential energy of a gas in a piston A system is a defined mass or volume of material that we will be investigating. Example 1.26: Nitrogen cooled in a closed vessel

A piston (diameter 5 cm; height 10 cm) containing a certain volume of air is placed 2 m Example 1.25: Water from a waterfall Nitrogen is stored in a 10 L flask at an initial pressure of 5.921 atm. Calculate the heat
above the ground. that is transferred when the nitrogen is cooled from 90 to 30°C.
a) Define a suitable reference point. Water falls from a 210 m waterfall. Given:
b) What is the potential energy of the gas in the piston? a) What is the potential energy of the water at the top of the waterfall? Cp [kJ/mol. °C] = 0.0290 + 0.2199 × 10-5T + 0.5723 × 10-8T2 – 2.871 × 10-12T3
c) The piston is moved and placed on the floor. What is the potential energy of the b) Assuming that all the energy is converted to kinetic energy, what is the water’s
gas at its new position? speed at the bottom of the waterfall? Solution:
d) While still on the ground, what is the potential energy of the gas if the piston is c) The terminal velocity of water is given as roughly 10 m/s (depending on the size From an energy balance that assumes no kinetic or potential energy:
0
compressed to halve its original height?* of the droplets). How does this compare to the answer for (b)? 𝑑𝑈
= I𝐻 +𝑄 +𝑊
e) Discuss the importance of defining a reference point. d) Assuming that the water droplet is only travelling at 10 m/s when it reaches the 𝑑𝑡
/1$
bottom of the waterfall, what happened to the remaining energy?
f) How does a system differ from and a reference point?
e) If the temperature of the water at the top of the waterfall is 25°C, calculate the For a closed system with no work added, this becomes:
temperature of the water at the bottom of the waterfall. Assumption: No water 𝑑𝑈
Solution: evaporates. =𝑄
a) The reference point is taken as the floor. 𝑑𝑡
f) If water evaporates, would the temperature in (e) be higher or lower? Explain.
Rearranging and rewriting for the definition of U:
b) Assuming:
- Mass of piston can be neglected Solution: 𝑄 = 𝑛 S 𝐶3 𝑑𝑇
- No heat transfer between system and surroundings a) 𝐸'! ()* = 𝑔ℎ()* = 9.8 𝑚𝑠 "# × 270 𝑚 = 2058 𝑚# 𝑠 "# 𝑜𝑟 𝑁𝑚/𝑘𝑔 𝑜𝑟 𝐽/𝑘𝑔

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 Energy balances – Problems

Cp [kJ/kg] = (4.2 – 2 × 10-3) T[K] c) Condensation point

Cv = Cp – R Hf0 = -285820 kJ/kmol d) Freezing point
= (0.0290 + 0.2199 × 10-5T + 0.5723 × 10-8T2 – 2.871 × 10-12T3) – (8.314 × 10-3) Molar mass of water: 18 kg/kmol e) Boiling point
= (0.02069 + 0.2199 × 10-5T + 0.5723 × 10-8T2 – 2.871 × 10-12T3) kJ/mol.°C f) Solid
Solution: g) Heat of vaporisation
!"
Therefore: "#545#%!#$%& .; h) Heat of condensation
6%
F9° =
Conversion: 𝐻 !' = −15878.9
$5
!#$%&
.< i) Heat of fusion
"4 "5 # "$# 6
𝑄 = 𝑛 S (0.02069 + 0.2199 × 10 𝑇 + 0.5723 × 10 𝑇 – 2.871 × 10 𝑇 )𝑑𝑇 j) Heat of solidification
7% =# k) Absolute zero temperature
"4
0.2199 × 10 F9° + 𝑚̇ × S 𝐶* 𝑑𝑇
𝐻 = 𝑚̇𝐻 l) Melting point
𝑄 = 𝑛 V0.02069(30 − 90) + (30# − 90#)
2 =$
0.5723 × 10"5 𝑘𝐽 𝑘𝑔 𝑘𝐽 Example 1.30: Steam table calculations involving interpolation
+ (306 − 906) 335630.9 = g15 × −15878.9 h
3 ℎ𝑟 ℎ𝑟 𝑘𝑔
2.871 × 10"$# 𝑘𝑔 =#
𝑘𝐽
− (308 − 908 )W + 60 × S (4.2 − 2 × 10"6)𝑇 ( ) Using the steam tables, calculate the following:
4 ℎ𝑟 #75 𝑘𝑔 1) Enthalpy of saturated water at 98 bar
𝑄 = 𝑛[−1.24921 𝑘𝐽/𝑚𝑜𝑙] 𝑘𝐽 𝑘𝑔 𝑘𝐽 2) Enthalpy of saturated steam at 131°C
335630.9 ℎ𝑟 − g15 ℎ𝑟 × −15878.9 𝑘𝑔 h 4.2 − 2 × 10"6 𝑘𝐽
= ij k × (𝑇# − 298)#l 3) Enthalpy of saturated steam at 8 bar and 240°C
From the ideal gas law: 15 2 ℎ𝑟
4) Internal energy of saturated steam at 0.05 bar and 190°C
𝑃𝑉 (5.921𝑎𝑡𝑚)(10.0𝐿) 4.2 − 2 × 10"6 5) Enthalpy of vaporisation for saturated system at a pressure of 178 bar
𝑛= = 𝑎𝑡𝑚 = 1.9877 𝑚𝑜𝑙 38254.28 = j k × (𝑇# − 298)#
𝑅𝑇 `0.08206𝐿. 𝑚𝑜𝑙. 𝐾b (363𝐾) 2 [kJ/kg]
18225 = (𝑇# − 298)#
And: 135 = 𝑇# − 298 Solution:
𝑄 = 1.9877[−1.24921] = −2.483 𝑘𝐽 𝑇# = 433𝐾 1) 1399.2 kJ/kg
𝑇# = 160 °𝐶 2) 2659.6 kJ/kg
3) 2928.8 kJ/kg
Example 1.27: Heat loss in a closed system with work
From steam table, at 2 bar (superheated steam): 4) 2647.4 kJ/kg
150°C 160°C 200°C 5) 819 kJ/kg
Calculate the total heat for a closed stationary system of 8lbs, when 2334 ft.lbf of work is
done on it. The internal energy of the system increases by 4 Btu/lbm. 0.9602 1.081
Given: 1 ft.lbf = 0.001285 BTU Example 1.31: Internal energy and enthalpy over phase change
By interpolation: Specific volume = 0.98436 m3/kg
Solution: A liquid at 180°C and 1 002.7 kPa has an internal energy of 762.0 kJ/kg and a specific
The energy balance assuming no kinetic or potential energy: Example 1.29: Labelling enthalpy-pressure diagram for water volume of 1.128 cm³/g.
0 1. What is its enthalpy?
𝑑𝑈
= I 𝐻/ + 𝑄 + 𝑊 2. The liquid is brought to the vapor state at 300°C and 1 500 kPa where its
𝑑𝑡 Given the enthalpy-temperature diagram for water below, label all unknowns.
/1$ internal energy is 2 784.4 kJ/kg, and its specific volume is 169.7 cm³/g.
For a closed system: Calculate ΔU and ΔH for the process.
𝑑𝑈
= 𝑄+𝑊 c b
𝑑𝑡 Solution:
g (from e à c) h (from c à e) 1. H = U + PV
Therefore:
𝑑𝑈 e
𝑄= −𝑊 Including the unit conversion:
𝑑𝑡 a
d H1 = 762 + (1 002.7 × [(1.28/1003).1000]) = 763.13 kJ/kg
Enthalpy

Substituting values: i (from là d) j (from d à l) .;

2. 𝑈# = 2 784.4 (𝑔𝑖𝑣𝑒𝑛)
𝐵𝑇𝑈 0.001285𝐵𝑇𝑈 .<
𝑄 = 8 𝑙𝑏. 4 − 2334 𝑓𝑡. 𝑙𝑏9 . = 29 𝐵𝑇𝑈 H2 = U2 + P2V2 = 2784.4 + (1500 × [(169.7/1003).1000]) = 3038.95 kJ/kg
𝑙𝑏- 1𝑓𝑡. 𝑙𝑏9 l
k f
∆𝑈 = 𝑈# − 𝑈$ = 2784.4 − 762.0 = 2022.4 𝑘𝐽/𝑘𝑔
Example 1.28: Specific volume from enthalpy calculation
∆𝐻 = 𝐻# − 𝐻$ = 3038.95 − 763.13 = 2275.82 𝑘𝐽/𝑘𝑔

A stream of water (15 kg/hr) is heated from 25°C to T2 at a constant pressure of 2 bar Temperature
such that the final enthalpy is 335630.9 kJ/hr. Calculate the specific volume of the water
at the new temperature.
Solution:
a) Liquid water
Given:
b) Superheated steam

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 – Problems

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