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Energy Balance - Introduction

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Energy Balances Introduction

1 ENERGY BALANCES
1.1 Introduction
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.

1.2 Basic Concepts

Definitions of Terms
Before being able to calculate an energy balance it is important to understand the terms needed for
such. These include terms which may already be familiar to you as in ()

Boundary
Closed (non-flow) system
Density
Energy
Enthalpy
Equilibrium
Equilibrium
Extensive property
Heat
Intensive property
Open (flow) system
Phase
Pressure
Property
Specific heat
Specific property
State
Steady state
Surroundings
System
Unsteady (transient) state
Work

Open System: Defined space where matter and energy can flow in and out.
Closed System: Defined space where only energy can flow in and out; not matter.
Isolated System: Defined space where neither matter nor energy can flow in or out.

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Energy Balances Introduction

Work, Energy and Heat

Work, heat and energy are all central concepts that are needed in this section.

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∆V), 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:

W = Wflow + W∆V + Ws + Wel + Wother 1.1

This is typically re-written as:

W = Wflow + Wn 1.2

Where:
Wn is all the non-flow work

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 + EK + ER + EP + Eel + ES + Eother 1.3

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Energy Balances Introduction

Heat
Heat is the disorganized transfer of energy that results due to a temperature gradient. Heat is not
included in the energy of a system since it is the transfer of energy between systems while energy that
part within a system.

For a closed system heat, energy and work are related by:
 E = Q + W 1.4

Where E = Ef – E0, or the change in energy from the initial to final states.

Internal Energy
For a closed system it was shown that:
 E = Q + W 1.5

Since energy was defined as:

E = U + EK + ER + EP + Eel + ES + Eother 1.6

For a system with no potential, kinetic, rotational etc. energy, this can be simplified to:
E=U 1.7

Therefore:
 U = Q + W 1.8

Strictly speaking, this should be written as:

dU = δQ + δW 1.9

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

For a constant volume (closed) system, we can simplify this as:

dU = δQ 1.10
Or
 U = Q 1.11

Since, from the work term below, all W terms are zero
W = Wflow + W∆V + Ws + Wel + Wother 1.12

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Energy Balances Introduction

Enthalpy
Enthalpy is defined as:
H = U + PV

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.

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)  H = 0.

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

Hf0 : Standard enthalpy of formation
0: standard state
f: formation

We can only add enthalpies which have the SAME basis.

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Energy Balances Introduction

Example:
CO(g)
𝑛̇ = 100 mol/min
T = 298.15 K
P = 1 bar

Calculate the enthalpy of this stream

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

Enthalpy is measure of energy. Hence units are in…

Enthalpy is an extensive property (depends on the amount of substance present)
Units: kJ; kJ/mol; kJ/kg; kJ/min

𝐻𝑓0 CO(g) = -110.53 kJ/mol

Enthalpy flow:
𝑚𝑜𝑙 𝑘𝐽
𝐻̇ (𝑘𝐽/𝑚𝑖𝑛) = 100 𝑥(−110.53)
𝑚𝑖𝑛 𝑚𝑜𝑙
𝑘𝐽
𝐻 ̇ (𝑘𝐽/𝑚𝑖𝑛) = −11 053
𝑚𝑖𝑛
𝑘𝐽
𝐻̇ (𝑘𝐽/𝑚𝑖𝑛) = −11. 053 𝑥 103
𝑚𝑖𝑛

The standard unit for energy is the Watt (or kilowatt) – 1 W = 1 J.s-1

Converting:
𝑘𝐽 1000 𝐽 1𝑚𝑖𝑛
−11. 053 𝑥 103 𝑥 𝑥 = −1.84 𝑥 105 𝐽/𝑠
𝑚𝑖𝑛 𝑘𝐽 60𝑠
= −1.84 𝑥 105 𝑊
= −184 𝑘𝑊

Therefore enthalpy is: -184 kW

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

Example:
CO(g)
𝑛̇ = 100 mol/min-1
T = 350 K
P = 1 bar

Calculate the enthalpy of this stream.

The reaction conditions are no longer at standard temperature and
pressure; therefore the standard heat of formation is no longer valid.
(It is only valid at standard conditions.). We need something else to
calculate the enthalpy at a different temperature.

To do this we use specific heat.

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.

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Energy Balances Introduction

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.

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

Definition:
∂H
Ĉp = ( )
∂T x̃,P

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

Ḣ = ṅ Hfθ
Enthalpy under standard conditions

T2
Ḣ = ṅ Hfθ + ṅ ∫ Ĉp dt
T1
Calculation of enthalpy under non-standard conditions
Where:
T1 = reference temperature
T2 = new temperature

T2 T2
∂H
∫ Ĉp dt = ∫ ( ) dt = H|T2 − H|T1
T1 T1 ∂T x̃,P
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:
T2
T
∫ Ĉp dt = Ĉp T| 2 = Ĉp (T2 − T1 ) = Ĉp ∆T
T1
T1

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

Example:
CO(g)
𝑛̇ = 100mol/min
T = 350 K
P = 1 bar
Cp = 29.14 J/K.mol

Calculate the enthalpy of this stream

∴ 𝐻̇ = −11.053 × 103 𝑘𝐽. 𝑚𝑖𝑛−1 + 𝑛̇ 𝐶̂𝑝 ∆𝑇

= −11.053 × 103 𝑘𝐽. 𝑚𝑖𝑛−1 + [100𝑚𝑜𝑙. 𝑚𝑖𝑛−1 × 29.14𝐽. 𝐾 −1 𝑚𝑜𝑙 −1 × (350 − 298.15)𝐾]
= −11.053 × 103 𝑘𝐽. 𝑚𝑖𝑛−1 + 151 090.9𝐽. 𝑚𝑖𝑛−1
= −11.053 × 103 𝑘𝐽. 𝑚𝑖𝑛−1 + 151.0909𝑘𝐽. 𝑚𝑖𝑛−1
= −10.902 × 103 𝑘𝐽. 𝑚𝑖𝑛−1

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  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 (x̃):

- 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

1.3 Steam Tables

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

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Energy Balances Introduction

- 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.

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.

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.

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.

Other Properties
In a similar way to 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.

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Energy Balances Introduction

Example:
Find:
(a) The enthalpy of water at 311°C and Ps.
(b) The enthalpy of steam at 90°C and Ps.
(c) The specific volume of steam at 30°C and Ps.
(d) The specific volume of water at 30°C and Ps.
(e) The enthalpy of steam at 10 bar and 300°C.
(f) The internal energy of steam at 0.525 bar and Ts.
(g) Heat of vaporisation at 201 bar and Ts.
(h) Enthalpy of steam at 175°C and 5 bar.
(i) The enthalpy of superheated steam at 360°C and 85 bar
(j) The saturated temperature and pressure at which the
steam has an enthalpy of 2700 kJ/kg

Solutions:
(a) 1408 kJ/kg
(b) 2659.7 kJ/kg
(c) 32.93 m3/kg
(d) 0.10044 × 10-2 m3/kg
(e) 3052 kJ/kg
(f) 2484.5 kJ/kg
(g) 5.72kJ/kg
(h) 2800.98 kJ/kg
(i) 3006.5 kJ/kg
(j) 115.77°C; 1.733 bar

Example:
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

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

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Energy Balances Introduction

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

For saturated steam:

P = 10 bar; Ts = 179.9°C; 𝑉̂𝑔 = 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 
P = 7.920 bar and 𝑉̂𝑙 = 0.1114 × 10-2 m3/kg
P = 10.03 bar and and 𝑉̂𝑙 = 0.1128 × 10-2 m3/kg

By interpolation:
(0.1128 × 10−2 − 0.1114 × 10−2 )𝑚3 (𝑉̂𝑙 − 0.01114 × 10−2 )𝑚3
𝑘𝑔 𝑘𝑔
=
(10.03 − 7.920)𝑏𝑎𝑟 (10 − 7.920)𝑏𝑎𝑟
(0.1128 × 10−2 − 0.1114 × 10−2 )𝑚3 /𝑘𝑔 × (10 − 7.920)
𝑉̂𝑙 = + 0.01114 × 10−2 𝑚3 /𝑘𝑔
(10.03 − 7.920)
𝑉̂𝑙 = 1.125 × 10−2 𝑚3 /𝑘𝑔

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

Total Volume balance: Vt = Vl + Vg [2]
Since we only have specific volumes, (2) becomes:
Mt𝑉̂t = Ml𝑉̂l + Mg𝑉̂g [3]

Assuming 1 kg of steam:
𝑀𝑡 𝑉̂𝑡 = 𝑀𝑙 𝑉
̂𝑙 + (𝑀𝑡 − 𝑀𝑙 ) 𝑉̂𝑔
̂
𝑀𝑡 𝑉𝑡 = 𝑀𝑙 𝑉̂𝑙 + 𝑀𝑡 𝑉̂𝑔 − 𝑀𝑙 𝑉̂𝑔
̂𝑙 − 𝑉̂𝑔 ) = 𝑀𝑡 (𝑉̂𝑡 − 𝑉̂𝑔 )
𝑀𝑙 (𝑉
Steam quality derivation
(0.02 − 0.1944)𝑚3 /𝑘𝑔
𝑀𝑙 = 1𝑘𝑔
(1.125 × 10−3 − 0.1944)𝑚3 /𝑘𝑔
𝑀𝑙 = 0.9024𝑘𝑔

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

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

m𝑔
x= 1
mT

Since the volume is constant:

V = V𝑙 + V𝑔 2

By definition:
̂
V = mV 3

Equation 2 becomes:
̂ mT = V
V ̂𝑙 m𝑙 + V
̂𝑔 m𝑔 4

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Energy Balances Introduction

Divide by mT
̂ mT
V ̂ 𝑙 m𝑙
V ̂ 𝑔 m𝑔
V
= + 5
mT mT mT
̂ ̂
̂ = V𝑙m𝑙 + V𝑔m𝑔
V 6
mT mT

From the definition of quality:

m𝑔
x= 1
mT

We obtain can also obtain:

mT mT m𝑔
−x = − 7
mT mT mT
mT − m𝑔
1−x= 8
mT
m𝑙
1−x= 9
mT

Substituting 1 and 9 into 6:

̂ = (1 − x). V
V ̂𝑙 + x. V
̂𝑔 10

And re-arranging:
̂=V
V ̂𝑙 − x. V
̂𝑙 + x. V
̂𝑔 11
̂ ̂ ̂ ̂
V − V𝑙 = x. (V𝑔 − V𝑙 ) 12
V̂ −V̂𝑙
x= ̂ 𝑔 −V
̂𝑙
13
V

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Energy Balances Introduction

1.4 General Energy Balance Equation

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 Mout

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

Energy balance becomes:

In = Out
Energyin = Energyout
Energy from flowin + Q̇ + Ẇ = Energy from flowout

Rearranging:
0 = Energy from flowin − Energy from flowout + Q̇ + Ẇ

Only true for steady state – if not at steady state:

(Change in Energy) = (Energy from flowin − Energy from flowout ) + Q̇ + Ẇ

Energy is going to be defined as the internal energy (U) of the system/flow terms:
dU
= (Uin − Uout ) + Q̇ + Ẇ
dt

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Energy Balances Introduction

From the definition of enthalpy:

Enthalpy: H = U + PV
Since U is not possible to measure we wish to replace with enthalpy.

Therefore:
U = H − PV

dU
= ((H − PV)in − (H − PV)out ) + Q̇ + Ẇ
dt

Rearranging:
dU
= (Hin − Hout ) + Q̇ + Ẇ + ẆPV
dt

n
dU
= ∑ Hi + Q̇ + Ẇ + ẆPV
dt
i=1

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

n
d(U + Ek + Ep )
= ∑(Hi + Ek + Ep ) + Q̇ + Ẇ + ẆPV
dt
i=1

Or:
v2
d (U + M ( 2 + φ)) n
v2
= ∑ Ṁ i (H
̂+ + φ) + Q̇ + Ẇ + ẆPV
dt 2 i
i=1

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:
n
dU
̂ ) + Q̇ + Ẇ + ẆPV
= ∑(MH
dt i
i=1

Or as a molar basis:
n
dU
= ∑ (NH ) + Q̇ + Ẇ + ẆPV
dt − i
i=1

Some common forms of the energy balance:

Closed system, N-SS
dU
= Q̇ + Ẇ + ẆPV
dt

Closed system, SS
0 = Q̇ + Ẇ + ẆPV

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Energy Balances Introduction

Open system, SS
n
̂ ) + Q̇ + Ẇ + ẆPV
0 = ∑(MH i
i=1

Adiabatic process
n
dU
̂ ) + Ẇ + ẆPV
= ∑(MH
dt i
i=1

1.5 Energy Balances for Non-Reacting Systems

Introduction

Example:
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  6 intervals (even number)
Therefore we can use Simpson’s

Now:
200
𝐻= ∫ 𝐶𝑝(𝑥)
20

𝑏 ℎ
Simpson’s Rule: ∫𝑎 𝑓(𝑥) ≈ [𝑓(𝑥1 ) + 4𝑓(𝑥2 ) + 2𝑓(𝑥3 ) + ⋯ + 2𝑓(𝑥𝑛−2 ) + 4. 𝑓(𝑥𝑛−1 ) + 𝑓(𝑥𝑛 )]
3

Therefore:
200
ℎ
𝐻= ∫ 𝐶𝑝(𝑥) ≈ [𝐶𝑝1 + 4𝐶𝑝2 + 2𝐶𝑝3 + 4𝐶𝑝4 + 2𝐶𝑝5 + 4𝐶𝑝6 + 𝐶𝑝7 ]
20 3
𝐻 ≈ 5305.6𝐽/𝑚𝑜𝑙

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.

230 200 230

𝐻= ∫ 𝐶𝑝(𝑥) ≈ [∫ 𝐶𝑝(𝑥)] + [∫ 𝐶𝑝(𝑥)]
20 20 𝑆𝑖𝑚𝑝𝑠𝑜𝑛′ 𝑠𝑅𝑢𝑙𝑒 200 𝑇𝑟𝑎𝑝𝑒𝑧𝑜𝑖𝑑𝑎𝑙 𝑅𝑢𝑙𝑒
ℎ
𝐻 ≈ 5305.6 + [𝐶𝑝7 + 𝐶𝑝8 ] 𝑇𝑟𝑎𝑝𝑒𝑧𝑜𝑖𝑑𝑎𝑙 𝑅𝑢𝑙𝑒
2
𝐻 ≈ 5305.6 + 902
𝐻 ≈ 6207𝐽/𝑚𝑜𝑙

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Energy Balances Introduction

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.

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).

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

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.

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.

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

Evaporation vs. Boiling

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

−1
Rln(P0 ) 1
TB = ( + )
∆Hvap T0

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
Hvap = the heat of vaporization of the liquid, J/mol
T0 = the given temperature, K

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 Energy Balances Introduction

1.6 Energy Balances for Reacting Systems

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.

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. (H − ) + 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.

1.7 Additional Reading

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, 1995. Thermodynamic and Transport Properties of Fluids (SI Units), 5th ed.,
Blackwell Publishing.
Sandler, SI, 2006. Chemical, biochemical, and Engineering Thermodynamics, 4th ed., Wiley.
Skogestad, S, 2009. Chemical and Energy Process Engineering, CRC Press, Taylor & Francis Group.

1
Lowry, HH (ed), 1945. Chemistry of Coal Utilization, Ch. 4, Wiley: New York

16
K. Harding University of the Witwatersrand, Johannesburg

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