CP 201: MATERIAL AND ENERGY BALANCES

2. If there is an exothermic reaction in the process; how can this energy be utilized.
CHAPTER 3: ENERGY AND ENERGY BALANCES
3. If exhaust gases are emitted at eleveted temperature from a combustion unit, can
the heat content of this gas be utilized somewhere in the process.
3.1 INTRODUCTION
4. How much fuel e.g. coal, natural gass, fuel oil, etc must be burnt to generate enough
Many materials processing operations require input of Energy of some sort. Energy can be steam for the process or running turbines to produce electricity?
used to increase reaction kinetics, provide the driving force that cause reactions to occur in
the first place, or melt or vaporise once or more phases on the system. Energy costs 5. How much heat is required to heat a process steam to the required reaction
money (it is expensive) thus wasting it is increasingly unacceplibe. As a result, the ability to temperature.
account for energy input and output for a system is as important to engineers as the use of
techique for materials accounting. 3.2 Forms of Energy

There are various sources of energy. Some of them have’nt been eploited and some have
been potentially exploited. For instance we havent yet learned how to use efficiently the
endless supply of ”free” energy provided by sources such as the sun, winds and tides.
Generation of energy using nuclear reactions is possible but the main problem is how to
dispose the radoactive waste obtained from the nuclear reactions.
The sources of Energy that have been potentially exploited include energy from water falls
(ie. Hydropower) and combustible fuels. However there are no enough water falls and
dams to meet world’s energy requirements. Also the natural resources for combustible
fuels is also limited.
Process industries have always recorganised that wasting energy leads to reduced profits.
This is due to dramatic increase in prices of fuel e.g. Natural gas and fuel oil. So, the only
remedy to these kind of situations is to use the energy efficiently.
In summary the sources of Energy are:
1) Solar, winds, and tides
2) Hydropower (water falls)
3) Nuclear reactions
4) Combustion of fuels
- Solid fuels e.g. Biomass, woods, coal, etc
- Gaseous fuels e.g. producer gas, Natural gas, Liqulified petroleum gas (LPG)
- Liquid fuelds e.g. Petrol, Diesel, etc.
The total energy of a system has mainly three components:ei
1. Kinetic Energy:
This is the energy due to the motion of the system as a whole relative to some
frame at reference (usually the earthis surface). It is given by
KE = ½ mv2, where m = Mass of the object (system and V = velocity.
2. Potentional Energy:
This is the energy jdue to the relative position of the system in a potential field (e.g
uniform gravitational field). It is given by: PE = mgh where; m = mass of the
objective, g = acceleration due to gravity, h = heigh or elevation relative to some
datum plane in the potential field.
3. Internal Energy:
This is the Energy due to the motion jof molecules relative to the center of mass of
the system, It is also due to rotational and vibrational motion and Electro magnetic
ineractions of the molacules. It is also due to the motion and interaction of the
atomic and sub atomic constituents of the molecules.
Thus the internal energy of a system is sometimes referred to as stored or chemical
energy of a system at rest undergoing processes which do not involved changes in
position, gravitational field, bulk velocity, and energy from electromatic field effects.
The interal energy U can be estimated as follows:

Thus, for an engineer designing a process his/her principal job would be to account i.e. U(v,T)
carefully for the energy that flows into and out of each process unit and to determine the
overall energy requirement for the process. This can be done by writing energy balances ⎛ ∂u ⎞ ⎛ ∂u ⎞
on the system in the same way as that for Material balance. dU = ⎜ ⎟ v dT =+ ⎜ ⎟ T dv (3.1)
⎝ ∂T ⎠ ⎝ ∂v ⎠
The typical questions for a design engineer would be:
⎛ ∂u ⎞
It can be noted that ⎜ ⎟ v = Cv = specific heat at constant volume
1. How can the process be designed to minimize the total energy requirements. ⎝ ∂T ⎠

57 58
 ⎛ ∂u ⎞ By its very definition, work indicates a transistion or motion and hence it can be
and for most of the processes ⎜ ⎟ T ≈ 0
⎝ ∂r ⎠ recorgnised as a form of energy in transition. When a system does work on its
surroundings it transfers to it a certain quantity of energy. Similarly, when the surroundings
and thus: do work on a system, the energy level of the system rises.
T2
U 2 – U1 = ∫ CvdT (3.2) By definition , W is positive for work going from the system to the surroundings. i.e. work
T1 done by the system to the surroundings is positive whereas W is negative for the work
coming from the surroundings to the system. .
It can therefore be noted that the internal energy can be calculated as a difference ∆ U,
relative to a reference state, but no absolute values of U can be calculated. In process By Field Effects
industries usually only these three forms of energy are considered. However there are In additional to mass, heat and work, energy can also be transformed by means of
other forms of energy that may be applicable to other fields of engineering. These include: electromagnetic radiation. A travelling wave of electromagnetic radiation impinging upon a
system will cause an energy transfer to that system. The mechanism for this transfer of
4. Electric and Magnetic field Energies energy is called Radiation. This is usually of less importance in chemical and process
These are stored energies due to electric and magnetic fields. Industries, however, it is very relevant in other fields of engineering.

3.3 Forms of Energy in Transition It can therefore be noted that, for a closed system i.e. no mass is transferred across its
system boundaries. The energy may be transferred between such a system and its
Energy can be exchanged between a system and its surroundings in essentially four ways: surroundings in two principal ways: That is as heat and as Work .

1. By transfer of mass
2. By performing work 3.4 The First Law of Thermodynamis for a Closed System
3. By transfer of heat
4. By field effects. The principle that underlies all energy balance calculations is the law of conservations of
energy, which states that energy can neither be created nor destroyed. This law is also
By transfer of mass called the first law of thermodynamics. In its general form, the first law state, that the rate
This is most easily visualized. It is clear that the energy inventory of a system can be at which energy (Kinetic, potential, and internal) is carried into a system by the input
changed by the transfer of mass because every mass is associated with a certain amount of streams plus the rate at which it enters as heat and work. Minus the rate at which it is
internal energy. For instance, if a unit mass of water is added to the system consisting of transported act of the system by the output streams equal to the rate of Accumulation of
a pool of water, the internal energy of the system must increase by at least the internal energy in the system. (i.e. Acc = Input – output) i.e.
energy of the unit mass added.
(Energy Accumulation) = (Energy input) – (Energy output) (3.4)
By Transfer of Heat
Heat is the energy that flows as a result of a temprature difference between a system and Now if we consider a closed system, i.e. no transfer of Mass across the system boundary,
its surroundings. The direction of flow is always form a higher temperature to a lower one. then energy can be exchanged between the system with its surroundings through only two
Heat is defined as positive when it is transferred to the system from the surroundings. The ways: i.e. by heat transfer and by performing work (of cause here we are assuming that
heat transfer mechanism that are now understood to cause this heat flow are conduction field effects are negligible).
and convection.
Consider a system in a state with initial energy inventory of EI, Suppose that the system
By Performing Work does work on its surrounding (let the work be W), suppose further that the system
Work is the energy that flows in response to any driving force other than a temperature exchanges heat with its surroundings (Q). As a result of this interchange of heat, work, the
difference, e.g. Force, Torque, or Voltage. In Mechanics, work is defined as the system will achieve a new state with energy inventory EF:
product of force and distance through which it acts:
W = F. ∆Z , if F is constant, or Since the energy is conserved: then: Input = output
(3.3a)
Z2
(EF - EI) = Q – W (3.5a)
W= ∫
Z1
FdZ , if F is variable over the distance distance Z1 to Z2 (3.3b)

59 60
 ∆E piston up so that the volume of gas expands from 0.1, to 0.2m3. Calculate the work done
by the gas on the piston if two different paths are used:
Q W
But ; Path A: Expassion occurs at constant pressure (P = 200 kpa)
Path B: Expansion occurs at constant tempreature (T = 300 K)
EF – EI = (Uf − Ui ) + (Kf − Ki ) + (Pf − Pi ) (3.5b)

Solution:
:. ∆U + ∆K + ∆P = Q − W (3.6)

Equation 3.6 represents the first law of thermodynamics for a closed system.
F = Force
Points to Note A = Surface area of the piston
expansion dz = Change in distance moved by the
1) The internal energy of a system (U) depends entirely on the chemical composition, V1=0.1 piston
V2=0.2
state of Aggregation, and temperature of the system materials. It is indipendent of Gas Gas
pressure, for ideal gases and also independent of pressure for liquids and solids. 300 K T2 = ?
200 kPa P2 = ?
Therefore, if no changes of temperature, phase or chemical composition occurs in
the process and if or ideal gases, then ∆U = O
State 1 State 2
T2
Recall that: ∆U = ∫
T1
CvdT , if T = constant then dT = 0;hence ∆U = 0 Fig. 3.1: Figure for example 3.1
2) If the system and the surroundings are at the same temperature, or if the system is
perfectly insultated then Q = 0, ie the system is said to be adiabatic.
state F v2 F
∫ . Adz = ∫ Pdv
state
Work (W) = ∫ F .dz = = Pressure
state1 state1 A v1 A
T system =T surroundings, ∆T = 0 Q = 0, Adz = dv change in Volume

Recall that: Path A: At constant temperature,

Q = AU (T 2 − T 1) W = P ∫ dv = P (V 2 − V 1)
v2
= 200 x 103 Pa x (0.2 – 0.1)m3
v1
(3.7) = 20 x103 Pa.m3 1 N/m2 m3 1J
Where: A = Surface area and U= Overall heat Transfer coefficient
1Pa 1Nm
3) Workdone (W) on or by a closed system is accompained by movement of the system
boundary against a resisting force. Thus if there are no moving parts pr generated W = 20 kJ
currents in a closed system, then W=O.

4) ∆P depends on changes in height, if no height changes then ∆P = 0 (Recall that Path B At constant temperature, PV = nRT , or P =
nRT
∆P = mg ∆ h) V

5) ∆ K depends on changes in velocity ( ∆ K = ½m ∆ v2), Thus if no velocity changes V2 nRT ⎛V ⎞ P1V1 ⎛V ⎞

then ∆ K = O W= ∫V1 V
⋅ dv = nRT In ⎜⎜ 2
⎝ V1
⎟⎟ =
⎠ RT
⋅ RT ⋅ In ⎜⎜ 2
⎝ V1
⎟⎟
⎠
Examples 3.1 Expansion of an ideal Gas
⎛V ⎞
Suppose that an ideal gas at 300K and 200Kpa is enclosed in a cylinder by a frictionaless
W = P1V1 In ⎜⎜ 2 ( ) ⎛ 0.2 ⎞
⎟⎟ = 200 x 10 3 (0.1) In ⎜ ⎟ = 13.86 kJ
⎝ V1 ⎠ ⎝ 0.1 ⎠
piston and the gas slowly forces the piston up so that the volume of gas slowly forces the
61 62
 Note here that the work is done by the gas on moving the piston. So W is positive
Example 3.2: according to our definition and sign of work.

Consider the following expansion process of a gas

Example 3.3

A 1 Kg mass of steam of water leaves the bottom outlet of a vertical pipe with avelocity of
2m/s and falls 100 m to a pool below. What is the velocity as it hits the pool?
Placed in 100oC
Clamp Solution: The initral and final states are shown in figure 3.3:
25oC Boiling water
Q absorbed by
Clamp removed
Gas = 2kJ
gas gas does 100J 1 Initial
Work in moving
1 kg
the piston
Write the Energy balance H2O
Equation for each of the two 2 m/s
stages of this process and in 100 m
each case solve for the
unknown energy term in the 100oC
Equations
2 Final

Fig. 3.2: Figure for example 3.2 Fig 3.3: Figure for example 3.3

Solution: Assuming that the 1kg mass of water is the clesed system and that there is no change of
internal energy (T = Constant). Then ∆K + ∆P = 0
Case 1: ∆ U + ∆ K + ∆ P = Q – W (Equation 3.6) W = 0 (no mechanical movements)
Q = 0 (no temperature differences)
∆K = 0 (The System is stationery)
∆P = 0 (No Change in height)
W = 0 (No mechanical movements)
1M
2
(V22 − V12 ) + mg (Z 2 − Z1 ) = 0; Z 2 − Z1 = 100m , V1 = 2 m s

V22 = 2g (100) + V12 = 2(9.81) (100) + 2 + 1965.33

Q ∆U = Q = 2 kJ
1

Case 2: ∆U + ∆K + ∆P = Q – W V2 = {1965.33 } 2 = 44.33 m

s

∆K = The system is stationery, no velocity changes

∆P = No height changes
3.5 Enthalpy and state functions
∆U = 0, T = Constant
Enthalpy is a thermodynamic variable which occurs frequently in Energy balances. It is
Q = W = 100 J , Q = 100 J
defined as follows: H = U + PV where U = Internal Energy, P = Pressure and V = Volume.
The Enthalpy (H) is actually the heat content of a system. For a pure substance, the

63 64
Enthalpy of a single phase can be expressed as a function of temperature and The variables such as specific enthalpy (H) and internal energy (U) as well as temperature,
pressure.That is H = H (T,P). pressure and density are called point functions or state variables meaning that their
values depend only on the state of the material (temperature, pressure, phase,
To calculate the Enthalpy per unit mass, the total derivative of H can be used i.e. composition) and NOT how the material reached that state. To illustrate this consider the
following case where a substance goes from state 1 to state 2. There are four possible
⎛ ∂Hˆ ⎞ ⎛ ∂Hˆ ⎞ rootes on which this can be achieved.
d Hˆ = ⎜⎜ ⎟ ⋅ dT + ⎜
⎟ ⎜ ∂p
⎟ ⋅ dp
⎟
⎝ ∂T ⎠p ⎝ ⎠T
(3.8) B
Recall that: T 2
⎛ ∂Ĥ ⎞
⎜ ⎟
⎜ ∂T ⎟ p = Cp (From thermodynamics class) C
⎝ ⎠
P = constant

and that: A
1
⎛ ∂Hˆ ⎞ T = constant
⎜ ⎟
⎜ ∂p ⎟ ≈ 0 : Since the pressure in most materials processing operations is
⎝ ⎠T
P
⎛ ∂Hˆ ⎞
constant. So ⎜⎜ ⎟ will almost negligible for most of the processes.
⎟
⎝ ∂p ⎠ T Fig 3.4: Behavior of state variables
Thus:
Route A: T =constant, P = Constant
T2 Route B: P = Constant, T = Constant
Hˆ − Hˆ = ∫ Cp dT
T1 Route C: Direct 1 2
(3.9) Route D: Wigly line 1 2

This will give Enthalpy change for the two states 1, and 2. Like Internal Energy (U), the Because ∆Ĥ is a state variable/function, then all of the above rootes should give the same
Enthalpy (H) has no absolute values. Only the difference ( ∆ H) can be calculated relative to result of ∆Ĥ . Also note that if a cyclic process is involved that is going from 1 to 2 and
a standard reference state. For instance, the reference conditions used in calculating back to 1
Enthapies of stream and water (in steam tables) are Oo C (32oF) and its vapour pressure.
This does not mean that the enthalpy at these conditions is zero, but merely that the i.e. 1 → 2 → 1, Then ∆Ĥ = 0. i.e.
enthalpy has been aibitarily assigned a value of zero at these conditions.

It can also be noted that during computation of Enthalpy changes, the reference conditions ∫ dHˆ = 0, (1 → 2 – 1); ∫ dUˆ = 0 (1 → 2 – 1)
cancel out as can be seen from the following: and ∫ dT = 0 (1-2-1)

Initial state of system: Final state of system

Thus most of the properties such as P, T, U, P (pressure), H etc are state variables and
depend only on the state of the substance of interest. And that the values for a difference
∆Hˆ 1 = Hˆ 1 − H ref ∆H 2 = Hˆ − Hˆ ref
in a point variable (state function) can be calculated by taking the value in the Final State
and Substracting the value in the Initial State regardless of the actual path.
Net Ethalpy change ∆H = ∆H 2 − ∆H 1 =
= (
Hˆ − Hˆ 2 ref ) - (Hˆ − Hˆ
1 ref )= Hˆ 2 − Hˆ 1 = ∆H 3.6 Head Capacities

The heat capacity is the amount of energy (Heat) required to increase the temperature of a
Point or State functions
substance by 1o (degrees). Thus one can provide this energy at constant pressure (so we

65 66
hace Cp) or at constant volume (so we have Cv) The two heat capacities are defined as
follows:
⎛ ∂Ĥ ⎞ ⎛ ∂Û ⎞ ˆ
Cp = ⎜⎜ ⎟ P and Cv ⎜
⎟
⎟
⎜ ∂Τ ⎟ V (3.10)
⎝ ∂Τ ⎠ ⎝ ⎠

For liquids and solids, the distruction between Cp and Cv is very little. This is because
liquids and solids do not change very much if the process is carried out at constant pressure
or volume. However for gases there is a large distinction between Cp and Cv.

i.e. For liquids and solids: Cp ≈ Cv (3.11a)

For Ideal gases: Cp = Cv + R (3.11b)

where R = ideal gas constant. It can also be shown that for Ideal gases
CP
Cp = γ = 1.4 (3.11c)
Cv
Liquid Gas
Since most of industrial processes occur at constant pressure (usually atmospheric
Solid II
pressure) values of Cp are frequently used in Energy balances, and Cv values are not
frequently used. Thus the Cp will be discussed in detail.

Cp is usually expressed as a function of temperature in the form of

Solid I
2
Cp = a + bT + CT +……….. or
Cp = a + bT + cT-2 + ……….. or
C
Cp = a + bT + + …………. T [K]
T
Fig. 3.5: Typical relationship of CP as a function of temperature
Where a, b, c, are constants and T is temperature in specified units. The units of p are
kJ Βtu J It can therefore be noted that:
normally or or
Kg mol.K 1b mol.0 F gmol 0C
1) The heat capacity function is continous only in the regions between the phase
The Cp Equations are normally tabulated in Literature. It is important to note that most of transitions.
these equations are empirical in nature, which means that there are no scientific principles 2) On each phase a Cp function has to be established.
behind their use. They have been selected just because they happened to fit the 3) It is not possible to have a Cp function valid from absolute zero to any temperature
experimental data over broad temperature ranges. (i.e. valid for all temperature ranges).

Also, when selecting these Equations from literature, it is very import to note the units of Thus, experimental data of Cp are needed for each phase transition so as to establish its
temperature that have to be used in the computation of Cp and also the final units of Cp. equation (function).

Cp values are always positive, so the value of the constant a is also always a positive value.
As long as there is no phase change, the values of Cp normally increase with increasing
temperature. The variation of Cp with temperature can be presented as follows:
Estimation of heat capacities
For accurate energy balance calculations, the heat capacity equations from literature have
to be used. However in the absence of this information, there are a number of equations

67 68
and estimation techniques that can be used to give estimates of heat capacities. These are Other methods for estimations of Cp values of different levels of complexity can be found in
discussed below. Literature such as: R.C. Reid, J.M. Prausnitz and B.E. Poling: The properties of gases and
liquids, 4th Edn, Mc Graw-Hill, New York, 1987.
Heat Capacities of Mixtures:
3.7 Calculation of Enthalpy Change (without phase change)
For ideal gas mixtures, the heat capacity of the mixture can be estimated from:
In this section we shall concentrate on how to calculate the ”Sensible heat” using the heat
n
capacity Equations for single phase problems. Sensible heat is the Enthalpy difference
Cpav= ∑y
i =1
i CPi (3.12)
(normally for a gas) between some reference temperature and the temperature of the
where: Material under consideration, excluding any enthalpy differences for phase changes that are
yi = Mole fraction of the component i termed as Latent heats. To examine the concept of sensible heat, let us examine the
energy profile for heating a liquid substance from the liquid state to vapour which can be
CPi = Heat capacity of component i presented as follows:

For liquids:
T
n
Cpav = ∑X
i =1
i Cpi (3.13)

where : T2

Xi = Weight fruction of component i Q3

Cpi = Cp of component i
T1 Q2

Most of Cp values for liquid hydrocarbons and organic liquids are tabulated in literature and Q1 Latent heat Sensible
hence they can be used. heat
T0
For Solids: Q1= mCP ∆T Q2= mλ Q3 = ∆H S

The simple Kopp’s rule can be used: This states that at room temperature, the sum of the
heat capacities of individual elements is approximately equal to the heat capacity of a solid
Q/∆H
compound.This is illustrated in example 3.4.
Fig. 3.6: Energy profile for heating a sustance from liquid to gaseous state
Example 3.4

Estimate the heat capacity of Na2SO4.10H2O at room temperature using the Kopp’s rule
Now if the heat capacity equation is given as:
From Literature, the heat capacities of Na, S, O and H are
Cal Cp = a + bT + CT2, Then
6.2, 5.1, 4.0, 2.3 respectively, thus:
gmol o C
∫ (a + bT + CT )dT
T2 T2
∆Hˆ s = ∫ = 2
Cal Cp dT
Cp Na 2 SO4 .10 H 2O = 2(6.2) + 1(5.4) + 14(4.0) + 20(2.3) = 119
T1 T1

gmol 0C
∆Hˆ S = a (T2 − T1 ) +
2
(
b 2
T2 − T1 +
2 C
3
)
T2 − T1
3
(3
) (3.14)

2 Na 1S (10+4) O 20 H The result is actually the area under the curve of the Cp equation under the limits of T1 and
T2

69 70
Example 3.5
This can be presented in a Tabular form as shown in Table 3.1
The following gas stream is emitted from a combustion chamber: CO2 = 9.2% mol, CO =
1.5% mol, O2 = 7.3% mol and N2 = 82.0% mol. If the temperature at the bottom and top Table 3.1; Calculations for example 3.5
of the stack are 550 oF and 200 oF respectively. Calculate the sensible heat of this gas per Component I i Ii ai Ii bi Ii Ci Ii di
1b mol. N2 0.82 5.6539 6.25 x 10-4 -5.75 x 10-8 -
O 0.073 0.51859 5.73 x 10--5 -4.04 x 10-9 -
Solution: Co2 0.092 0.7772 5.30 x 10-4 -1.99 x 10-7 2.814 x 10-11
CO 0.015 0.10298 1.2 x 10-5 -1.11 x 10-9 -
Total 1.00 7.053 1.22 x 10-3 -2.61 x 10-7 2.814 x 10-11

Thus: C p = 7.05 + 1.22 x 10-3T – 2.61 x 10-7T2 + 2.814 x 10-11T3

1.22 x 10 −3
Q ∆H = ∫ C pdT = 7.053 (200 – 550) +
200
(2002 – 5502) +
200oF 550 2
Stack 2.61 x 10 −7 2.814 x 10 −11
- (2003 – 5503) + (2004 – 5504)
3 4

Combustion ∆Hˆ s = ? Btu

FG ∆H = − 2.6159 x 10 3 ≈ − 2616
Chamber 550oF 1b mol of gas

9.2% CO2
1.5% CO
Example 3.6 Cooling of an Ideal gas
7.3% O2
82.0% N2
Assuming ideal behaviour, calculate the heat that must be transferred in each of the
Fig. 3.7: Figure for example 3.5 following cases:

⎛ Btu ⎞ 1. A stream of Nitrogen flowing at a rate of 100 mol/min is heated from 20 to 100oC at
The heat capacity equations from Table E .2 (David Himmelblau’s book), ToF, Cp ⎜ o ⎟ constant pressure.
⎝ 1bmol F ⎠
2. Nitrogen contained in a 5 liter flask at an initial pressure of 3 bars is cooled from 90
are as follows: to 30oC.
N2: Cp = 6.895 + 0.7624 x 10-3T – 0.7009 x 10-7T2 T2
O2: Cp = 7.104 + 0.7851 x 10-3T – 0.5528 x 10-7T2 Case 1: Qˆ = ∆Hˆ = ∫
T1
CpdT
CO2: Cp = 8.448 + 5.757 x 10-3T – 21.59 x 10-7T2 + 3.049 x 10-10T3
CO: Cp = 6.865 + 0.8024 x 10-3T – 0.7367 x 10-7T2 From literature: CpN2 = 29.0 + 0.2199 x 10-2T + 0.5723 x 10-5T2 – 2.871 x 10-9T3
J
Basis:1 1bmol of the Gas Where T is in oC and Cp in
mol o C
4
C p = ∑ I i Cp i
T2 T2
∆H s = ∫ ni Cpi dT = ∫ Cp dT where: 0.2199 x 10 −2 0.5723 x 10 −5
T1 T1
i =1 ∆Ĥ = 29.0 [100 – 20] + [1002 – 202] + [1003 – 203]
2 3
N2 = IN 2 Cp N 2 = 0.82 [Cp ] ,
N2 O2 = IO 2 Cp O2 [
= 0.073 Cp O2 ] - 2.871 x 10-9 [1004 - 204]/4 = 2332
J
mol
CO: = I CO. Cp CO = 0.015 [CpCO ] , CO2 = I CO 2 [
Cp CO2 = 0.092 Cp CO2 ]
71 72
With the given flow rate: 100 mol ( min
)
Example 3.7
J mol J
∆H = 2332 x 100 = 2.332 x 105
mol min min Let us calculate the sensible heat of example 3.5 using the Tabulated Data presented in
Table 4.3 (Page 390) in David Himmelblau’s book.
Q = ∆H 2.332 x 10 5 J
min
T1 = 550oF = 550 + 460 = 1010oR
T2 = 200oF = 200 + 460 = 660oR
Case 2:
The Enthalpies of different species at these temperatures have to be obtained by
In this case the cooling process is at constant volume (5 liters): Thus we hace to evaluate interpolation:
∆U .
For N2 at 660oR, 600 → 751.9
T2 = 30
∆Uˆ = Qˆ ∫ T1 = 90
CvdT , From ideal gas behaviour Cp - Cv = R or Cv = Cp – R 660 → HN2, 660
700 → 1,450
J
or R = 8.314 60
Q H N 2 , 660 o R = (1,450 – 751.9) + 751.9 = 1171 Btu
mol. K 100 mol
o
HO2 , 660 R = 60 (1471 – 758.8) + 758.8 = 1186 Btu
Cv = (29.0 – 8.314) + 2.199 x 10-3T + 5.723 x 10-6T2 – 2.871 x 10-9T3 100 mol
2.199 x10 −3
[ 5.723x10 −6
] [ ] H CO2 ,660 R = 0.6 (1914 – 963) + 963 = 1534
o Btu
Qˆ = 20.686 [30 − 90] + 30 2 − 90 2 + 30 3 − 90 3 mol
2 3
H CO , 660 o R = 0.6 (1451 – 752.4) + 752.4 = 1172 Btu
− 2.871x10 −9
[ ] 3 mol
30 4 − 90 4 = −1.25 x10 J 10
4 mol HN 2 , 1010 R =
o
(4,285 – 3,565) + 3565 = 3637 Btu
100 mol
Now, using the ideal gas law, the number of moles can be established: H O2 ,1010 o R = 0.1 (4443 – 3680) + 3680 = 3756 Btu
mol
PV (3.0 ba/ r ) (5.0 lite/ rs ) H CO2 , 1010 O R = 0.1 (6167 – 5046) + 5046 = 5158 Btu
mol
I= = = 0.497 mol
RT lite/ r.ba/ r HCO, 1010oR = 0.1 (4304 – 3580) + 3580 = 3652 Btu
0.08314 x 363 K/ mol
mol. K/
Q = n. ∆Uˆ = 0.497/mol x (-1.25 x 103 J
mol
) = -621 J ( ) ( ) (
∆H = I N 2 H N 2 , 660 − H N 2 ,1010 + I O2 H O2 , 660 − H O2 ,1010 + I CO2 H CO2 ,660 − H CO2 ,1010 )
Q = − 621 J + I CO (H CO ,660 − H CO ,1010 )

∆H = 0.82 (1171 − 3637 ) + 0.073 (1186 − 3756 ) + 0.092 (1534 − 5158)

Calculation of Enthalpy Changes Using Tabular Data Btu
0.015 (1172 – 3652) = -2580.34
1b mol gas
As we have seen calculation of Enthalpy changes using the Cp Equations are cumbersome Btu
and Time involving. Thus, it is sometimes convinient using tables or Tabulated Data. ∆H = − 2580.34
1b mol of gas
Tables can cover ranges of physical properties beyond the range applicable for a single
equation. Because the most commonly measured properties are temperature and pressure,
Tables for pure compounds are usually organised in colums and rows with temperature and
pressure being the independent variables. If the interval between table entries are dose
enough, linear interporation between entries is reasonably accurate.
73 74
If the above result is compared with – 2616 Btu it can be observed that the error
1b mol gas Steam at 10 bars (absolute pressure), 180oC is fed to a turbine at a rate of 2000 kg/h. The
is approximately 1.4%. Suggesting that the results are reasonably close. turbine operation is adiabatic (dQ = 0) and the effluent is saturated steam at 1,0 bar.
Calculate the work output of the turbine in Kilo walts, neglecting Kinetic and Potential
Calculation of Enthalpy Changes Using Steam Tables Energy changes.

The most complete and precisely known tabulations of the Enthalpy and internal energy Solution
functions are those of water. This came about not only because water is such an abundant
substance but also because water, especially in its vapour form, has been the prime Steam in Steam out
working fluid for devices such as steam engines and steam turbines. Precise design of Turbine H2=?
these devices require accurate values of the state functions (enthalpy, internal Energy, etc) 2000 kg/h 1.0 bar
as well as the equation of state. Extensive and very detailed tabulation of the H1 =?
thermodynamic properties of liquid water and its vapour form, commonly called steam, can 10 bar, 180 oC W
be found in the compilation due to G.F.C. Rogers and Y.R. Mayhew, 4th Edition blackwell dQ = 0
publishers, 1992.
Fig. 3.8: Figure for example 3.9
Before proceeding to discuss the contents of these tables let us briefly review some of the
terminology used in steam calculations: Recall that water can exist in solid (ice), liquid and The Energy conservation equation suggests that:
vapour (or steam) phases and that under certain ranges of conditions these three phases
will exist in Equilibrium. At a given pressure, liquid water below its boiling or 0 0
saturation temperature is referred to as Unsaturated liquid. Liquid water at its ∆U + ∆ K + ∆ P = Q-W
boiling point/temperature is referred to a saturated steam. And the vapour
heated beyond the boiling point is that referred to as superheated steam. ∆U = Q − W , Recall that H = U + PV and
Superheated steam is usually characterized by a quantity called degree of superheat. 0 0
The degree of superheat is equal to the number of temperature degrees that the steam is
dH = du + PdV + VdP (Total derivative of H)
aboveits saturation or boiling temperature at the given pressure. In these steam Tables the
Subscript S usually referres to saturation (e.g TS, PS) subscript referrs to fluid and g referrs Thus for process involving negligible changes in volume and pressure,
to gas (vapour);
then dH = du
Example 3.8 Q dH = du = Q − W , Since Q = 0 , Then:
o o
Saturated water at 127 C and 2.5 bar is heated to 204 C and 17 bars. What are ∆Ĥ and −W = dH (
= m ∗ Hˆ 2 − Hˆ 1 )
o
∆Û in kJ ? From steam Tables: (180 C, 10 bars): H1 = 2778 kJ
Kg Kg
Saturated steam at 1.0 bar: H2 = 2675 kJ
Kg
Solution: From steam Tables
Q − W = (2675 − 2778) kJ
kg kJ 1h
⎛ kJ ⎞ = − 206,000
At 127oC and 2.5 bar h f ⎛⎜ kJ ⎞⎟ = 535, x 2000 .
U f ⎜⎜ ⎟⎟ = 535 Kg h h 36005
⎝ Kg ⎠ ⎝ Kg ⎠
⎛ kJ ⎞ ⎛ It ispositive indicating that the ⎞
At 204oC and 17 bar h f = 872 ⎜⎜ ⎟⎟, U f = 870 kJ W = 57.2 kW ⎜⎜ ⎟⎟
⎝ Kg ⎠ Kg
⎝ work is coming from the Turbine. ⎠
∆Hˆ = 872 − 535 = 337 kJ
Kg
Example 3.10
∆Uˆ = 870 − 535 = 335 kJ
Kg
Two streams of water are mixed to form the feed to a boiler. Process data are given as
follows:
Example 3.9 Feed stream 1: 120 kg/min at 30oC

75 76
Feed stream 2: 175 kg/min at 65oC The cross-sectional Area of the pipe = ∏ R 2
Boiler Pressure: 17 bars (absolute) A = 3.14 x (0.03)2 = 2.83 x 10-3 m2 = A
ms∗ ⋅ Vs
The existing stream emerges from the boiler through a 6cm inside diameter pipe. Calculate Steam velocity, Vs = , where Vs is the specific volume of steam. From steam
A
the required heat input to the boiler in kJ/min. If the emerging stream is saturated at the o 3
boiler pressure. Neglect Kinetic Energies of the liquid inlet streams. Tables at 17 bar, 204.3 C steam has specific volume of 0.1167 m
kg
/ / in
3
kg/ m 1 1m M
Solution: Basis: 1 minute V2 = 295 x 0.1167 x x = 203
min/ kg 2.83x10 −3 m
/
2
60 S S
F1 = 120 kg H2O (l) kJ ⎧ kg m 2 ⎫ ⎧ kg m m ⎫
x 295 x (203) = 6080
1
∆K = ⋅ ⎬ = ⎨ 2 •
2
30 ºC ⎨ ⎬
2 min ⎩ min S 2 ⎭ ⎩ S min ⎭
P
hence, Q = ∆H + ∆K = 7.62 x 105 + 6080
Boiler
295 kg H2O vapour Q = 7.68 x 105 kJ
min
17 saturated steam
F2 = 175 kg H2O (l) 6 cm ID pipe
65 ºC Q 3.8 Enthalpy changes for phase Transitions

Fig. 3.9: Figure for example 3.10 In the previous discussions (see section 3.6) we have observed that the heat capacity
functions are discontious at the point of phase transitions. The name that is usually given
to the enthalpy changes for these phase transitions is Latent heat changes. Latent
Enthalpies from steam Tables: meaning ”hidden”, in the sense that, a substance (e.g. water) can absorb a large
amount of heat without any noticeable or significant change in temperature.
This absorbed heat is called latent heat.
At 30oC, hf = 125.7 kJ , At 65oC, hf = 272.0 kJ , At 17 bar, 204.3oC, hg = 2795
Kg Kg
kJ
kJ
Kg e.g. Ice (solid H2O) at OoC can absorb ≈ 334 without undergoing temperature or
kg
Recall the Energy conservation Equation: kJ
0 0 0 pressure rise. Similarly liquid water at 1 atmosphere can absorb ≈ 2256 before
kg
∆H + ∆ K + ∆P = Q–W
temperature and pressure will change. The various enthalpy changes of this kind are
∆P = 0: No height changes termed as follows:
W = 0: No Mechanical movements
Q = ∆H + ∆K Phase Change Enthalpy change
Solid to liquid Latent heat of fussion
Liquid to vapour Latent heat of vapourisation
∆H = ∑I
outlet
i Hi - ∑I
inlet
i Hi
Vapour to liquid Latent heat of condersation
Solid to vapour Latent heat of sublimation
∆H = (295 x 2795) - ((120 x 125.7 ) + (175 x 272.0 ))
The latent heats for the various phase changes can easily be depicted if on an enthalpy
change – Temperature profile as that indicated below:
∆H = 7.62 x 10 kJ 5
min
⎛ Neglecting Kinetic ⎞
m2 (V22 − V12 ) ,
1
∆K = V1 ≅ 0 ⎜⎜ ⎟⎟
2 ⎝ Energy of Inlet Streams ⎠ Entahlpy vapour
1 [J/g]
∆K = ms Vs2 Subscripts referrs to steam.
2
So, we have to evaluate the exit velocity of steam, Vs. Latent heat
77 78
 of vapourisation/condensation
liquid ∆Hˆ V ∆Hˆ V
log10 P ∗ = − + B’ or ln (P ∗) = - + B’ (3.16)
2.303 RT RT

Latent heat
where B’ is a constant that varies from one substance to another P* = vapour pressure, T =
solid Of fussion
absolute temperature, ∆Ĥ V = Molar latent heat of vapourisation at T, R = Universal gas
constant. From this equation it is apparent that a plot of ln (P*) Versus I will give a
T
melting boiling Temperature [K] ∆Hˆ V
straight line of which the slope will be - and the y intercept will give B’.
point point R

Fig. 3.10: Various Phase changes for substances The values of ln (P*) can be evaluated using the well-known Antonie equation: i.e.

The various types of latent heats of pure substances are usually tabulated in literature. The B
ln (P*) = A - (3.17)
symbols that are normally used for latent heats are ∆Ĥ , L, λ , Λ , and hfg (in steam tables). C +T
In the absence of these tabulated values or experimental values. , the following
approximate methods can be used to provide an estimate of the molar latent heats. Note where: P* = Vapour pressure, [mmHg], T = Absolute temperature, [K]
that latent heats are normally large amounts of Energy. Therefore it is very important to
estimate them properly otherwise they can lead to abnomous errors in energy balances. A,B,C = Are constants which differ from one substance to another. They are normally
tabulated in literature for various substances.
3.8.1 Estimation of Latent heat of fusion
If follows from the Clausius – Clapeyron Equation that if the vapour pressures of a
There is no accurate and simple way of estimating. ∆ Hfusion. However the latent heat of substance at the temperatures T1 and T2 are known (normally in a very small interval of
fusion for many elements and compounds can roughly be estimated using: Temperature) then; ∆Ĥ V can be computed directly without making a plot, i.e.

⎧2 − 3 for Elements ⎛ P *⎞ ∆Hˆ V ⎡1 1⎤

∆Ĥ f ⎪ In ⎜⎜ 1 ⎟⎟ = ⎢ − ⎥ (3.18a)
= Constant = ⎨5 − 7 for Inorganic compunds (3.15) ⎝ P2 * ⎠ R ⎣ 2
T T1⎦
Tf ⎪9 − 11 for Organic compounds
⎩
P1 ∗ ∆Hˆ V ⎡1 1⎤
Or log10 = ⎢ − ⎥ (3.18b)
where: ∆Ĥ f = Molar Latent heat of fusuion, ⎡Cal ⎤ P2 ∗ 2.303 R ⎣ 2
T T1⎦
⎢⎣ g mol ⎥⎦
Tf = Melting point, [K]
Using Chen’s Equation:

⎡ ⎛T ⎞ ⎤
3.8.2 Estimation of Latent heat of Vapourisation Tb ⎢0.0331 ⎜⎜ b ⎟⎟ + (0.0297 log10 Pc ) − 0.0327⎥
⎣ ⎝ Tc ⎠ ⎦
∆Ĥ V = (3.19)
Three methods are discussed here for estimation of ∆Ĥ V . These are: ⎛ Tb ⎞
1.07 − ⎜⎜ ⎟⎟
⎝ Tc ⎠
1. Using the clausius-clapeyron Equation
2. Using the Chen’s Equation ⎡ kJ ⎤
Where: ∆Ĥ V = Latent heat of vapourisation in ⎢ ⎥
3. Using the Watson’s Equation ⎣ g mol ⎦
Tb = Normal boiling point in K [K]
Clausius-Clapeyron Equation:
Pc = Critical pressure in atmospheres [atm]
The equation can be presented as follows:
79 80
 8.314 x 4426.483 kJ J
∆Ĥ V = = 36.80 , R = 8.314
Using the Watson’s Equation: 1000 gmol gmol K
0.38
∆Hˆ V2 ⎡1 − Tr2 ⎤
0.38
⎡ T − T2 ⎤ kJ
= ⎢ ⎥ = ⎢ C ⎥ (3.20) ∆Hˆ V = 36.80
∆Hˆ ⎣⎢ 1 − Tr1 ⎥⎦ ⎣ TC − T1 ⎦
V1
gmol

Where: ∆Hˆ V2 = Latent heat of vapourisation of pure liquid at T2 b) Chen’s Equation:

Tb
=
337.9
= 0.6584
∆Hˆ = Latent of vapourisation of pure liquid at T1 TC 513.2
V1

Tr = Reduced Temperature T/Tc

337.9 [0.0331 x 0.6584 − 0.0327 + 0.0297 log 78.5]
Tc = Critical Temperature. ∆Ĥ V =
1.07 − 0.6584
Example 3.11
∆Hˆ V = 37.25 kJ
gmol
The normal boiling point of methanol (CH3OH) is 337.9 K and the critical temperature of
this substance is 513.2 K. Estimate the heat of vapourisation of methanol at 90oC. (363
K). Using: c) Watson Equation:
0.38
⎡ 513.2 − 363 ⎤ kJ
a) Clausius – Clapeyron Equation ∆Hˆ V2 = 35.3 ⎢ ⎥ = 33.87
b) Chen’s Equation ⎣ 513.2 − 337.9 ⎦ gmol
c) Watson’s Equation
It can be noted that the results are within ± 10%.
Solution:
To this point, we are now well equipped to handle calculations that involve Enthalpy
Data for Methanol: changes with phase transitions. Remmembering that Enthalpy is a state function, thus
Tb = 337.9 K; Tc = 513.2 K; Pc = 78.5 atm [from Table D1, Himmelblau’s book, Pg. 667], knowledge of the initial and final state will suffice for the actual computation. The path on
∆Ĥvap , at Tb = 35.3
kJ
[from the same Table]. Also from Appendix G, (Pg. 685). which it has been used to arrive at the final state is immaterial (not important) in these
gmol computations.
The appropriate Antonie equation for this substance can therefore be writen as:
Example 3.12

In (P ∗) = 18.5875 -
3626.55
T − 34.29 Compute the Enthalpy change of 1 kg of water from ice at 0oC to vapour at 120oC and 100
kPa.
a) Using the Clausius – Clapeyron Equation
Solution:
Let us make T1 = 360 K and T2 = 363 K such that ∆ T = 3 K;
Q In (P1 ∗) = 18.5875 -
3626.55
= 7.4532, P1 ∗ = 1725.39 mmHg ∆Ĥ Overall = ∆Hˆ fusion at 0o C + ∆Hˆ Liquid 0 →100o C + ∆Hˆ Vapourisation at 100o C + ∆Hˆ Vapour 100→120o C
360 − 34.29
From steam Tables:
In (P2 ∗) = 18.5875 -
3626.55
= 7.5548, P2 ∗ = 1909.94 mmHg ∆H fussion = 335 J at 0oC and P* = 101.3 k Pa, ∆Ĥ V = 2256.7 J at 100oC (101.3 k
363 − 34.29 g g
Pa)
Thus using: The heat capacity Equations can be obtained from Table E.1 (David Himmelblau’s book).
⎛ P ∗⎞ ∆Hˆ V ⎡ 1 1⎤ ∆Hˆ V ⎡ 1 1 ⎤
In ⎜⎜ 1 ⎟⎟ = ⎢ − ⎥ = = ⎢ − ⎥
∗
⎝ 2 ⎠
P R ⎣ 2
T T1⎦ R ⎣ 363 360 ⎦ ⎡ J ⎤ -2 -5
Cp (liquid) = ⎢ ⎥ = 18.296 + 47.212 x 10 Tk – 133.88 x 10 TK
2

⎣ gmol K ⎦

81 82
 + 1314.2 x 10-9 TK3 , TK in [K]

CpVapour ⎡ J ⎤ = 33.46 + 0.688 x 10-2 T +0.7604x10-5 T 2 O

200oF
⎢⎣ gmol K ⎥⎦ OC C

-9 o
- 3.593 x 10 TOC , TOC in [ C]
3 Stack

∫ (18,296 + 47.212 x 10 TK − 133.88 x 10 −5 TK2 + 1314.2 x10 −9 TK3 )

373 dT
−2
Q ∆Hˆ liquid 0o →100o C =
273
Combustion ∆Hˆ s = ?
Chamber FG 550oF
1 ⎡
∆Ĥ = ⎢18.296(373 − 273) +
18 ⎣
47.212 x10 −2
2
373 2 − 273 2 − [
133.88 x10 −5
3
3733 − 2733 ] ( )
9.2% CO2
1.5% CO
1314.2 x10 −9 ⎤
+ (
373 4 − 273 4 ⎥ ) J
g
7.3% O2
82.0% N2
4 ⎦
The heat capacity equations from Table E o 2 (David Himmelblau’s book), ToF, Cp
∆Hˆ liquid 0→100o C = 418.6 J or 418.59 J ⎛ Btu ⎞
g g
⎜ o ⎟ are as follows:
⎝ 1bmol F ⎠
1 ⎡ 120
CpVapour dT ⎤
18 ⎢⎣ ∫100
∆Hˆ Vapour 100−120o C = N2: Cp = 6.895 + 0.7624 x 10-3T – 0.7009 x 10-7T2
⎦⎥
O2: Cp = 7.104 + 0.7851 x 10-3T – 0.5528 x 10-7T2
1 ⎡ 0.688 x10 −2
(120 2 −100 2 )+ 0.76043 x10 (120 3 − 100 3 ) − 3.5934x10 ⎤⎥
−5 −9
CO2: Cp = 8.448 + 5.757 x 10-3T – 21.59 x 10-7T2 + 3.049 x 10-10T3
⎢33.46 (120 − 100 ) + CO: Cp = 6.865 + 0.8024 x 10-3T – 0.7367 x 10-7T2
18 ⎣ 2 ⎦
(120 4
)
− 100 4 = 38.116 J
g
Basis:1 1bmol of the Gas
∆Ĥ Overall = 335 + 418.59 + 2256.7 + 38.116 ≈ 3048 J 4
C p = ∑ I i Cpi
g T2 T2
∆H s = ∫ ni Cpi dT = ∫ Cp dT where:
kJ T1 T1
i =1
∆Hˆ Overall = 3048
kg
N2 = IN 2 Cp N 2 = 0.82 [Cp ] ,
N2 O2 = IO 2 Cp O2 [
= 0.073 Cp O2 ]
If steam Tables are used for calculation of this Enthalpy change, Then:
CO: = I CO. Cp CO = 0.015 [CpCO ] , CO2 = I CO 2 [
Cp CO2 = 0.092 Cp CO2 ]
(
∆Ĥ Overall = ∆H fusion + h f100 − h f 0 + ∆H Vap + ) (h g120 − hg100 )
This can be presented in a Tabular form as shown below:
kJ kJ kJ kJ
∆H fussion = 335 , h f ,100 0 C = 419.10 , h f ,0 0 C = 0 , ∆H vap = 2256.7 Component Ii Ii ai Ii bi Ii Ci Ii di
kg kg kg kg
N2 0.82 5.6539 6.25 x 10-4 -5.75 x 10-8 -
∆H = 335 + (419.1 – 0) + 2256.7 + (2707 – 2675) O 0.073 0.51859 5.73 x 10--5 -4.04 x 10-9 -
Co2 0.092 0.7772 5.30 x 10-4 -1.99 x 10-7 2.814 x 10-11
kJ CO 0.015 0.10298 1.2 x 10-5 -1.11 x 10-9 -
∆H = 3042 Total 1.00 7.053 1.22 x 10-3 -2.61 x 10-7 2.814 x 10-11
kg

Thus: C p = 7.05 + 1.22 x 10-3T – 2.61 x 10-7T2 + 2.814 x 10-11T3

83 84
 1.22 x 10 −3 T2 = 30
∆Uˆ = Qˆ ∫ CvdT , From ideal gas behaviour Cp - Cv = R or Cv = Cp – R
200
Q ∆H = ∫ C pdT = 7.053 (200 – 550) + (2002 – 5502) + T1 = 90
550 2
2.61 x 10 −7 2.814 x 10 −11
- (2003 – 5503) + (2004 – 5504) J
3 4 or R = 8.314
mol. K
Btu
∆H = − 2.6159 x 10 3 ≈ − 2616 Cv = (29.0 – 8.314) + 2.199 x 10-3T + 5.723 x 10-6T2 – 2.871 x 10-9T3
1b mol of gas
Qˆ = 20.686 [30 − 90] +
2.199 x10 −3
2
[
30 2 − 90 2 + ]
5.723 x10 −6
3
[
30 3 − 90 3]
Example 3.6 Cooling of an Ideal gas
− 2.871x10 −9
4
[ ]
30 4 − 90 4 = −1.25 x10 J
3

mol
Assuming ideal behaviour, calculate the heat that must be transferred in each of the
following cases: Now, using the ideal gas law, the number of moles can be established:

3. A stream of Nitrogen flowing at a rate of 100 mol/min is heated from 20 to 100oC at I=

PV
=
(3.0 ba/ r ) (5.0 lite/ rs )
= 0.497 mol
constant pressure. RT lite/ r.ba/ r
0.08314 x 363 K/
4. Nitrogen contained in a 5 liter flask at an initial pressure of 3 bars is cooled from 90 mol. K/
to 30oC. Q = n. ∆Uˆ = 0.497/mol x (-1.25 x 103 J ) = -621 J
mol
T2
Case 1: Qˆ = ∆Hˆ = ∫
T1
CpdT Q = − 621 J

From literature: CpN2 = 29.0 + 0.2199 x 10-2T + 0.5723 x 10-5T2 – 2.871 x 10-9T3
J Calculation of Enthalpy Changes Using Tabular Data
Where T is in oC and Cp in
mol o C As we have seen calculation of Enthalpy changes using the Cp Equations are cumbersome
and Time involving. Thus, it is sometimes convinient using tables or Tabulated Data.
0.2199 x 10 −2 0.5723 x 10 −5 Tables can cover ranges of physical properties beyond the range applicable for a single
∆Ĥ = 29.0 [100 – 20] + [1002 – 202] + [1003 – 203] equation. Because the most commonly measured properties are temperature and pressure,
2 3
Tables for pure compounds are usually organised in colums and rows with temperature and
J3 pressure being the independent variables. If the interval between table entries are dose
- 2.871 x 10-9 [1004 - 204]/4 = 2332
mol enough, linear interporation between entries is reasonably accurate.

With the given flow rate: 100 mol ( min

) Example 3.7

Let us calculate the sensible heat of example 3.5 using the Tabulated Data presented in
J mol J
∆H = 2332 x 100 = 2.332 x 105 Table 4.3 (Page 390) in David Himmelblau’s book.
mol min min
T1 = 550oF = 550 + 460 = 1010oR
Q = ∆H 2.332 x 10 5 J T2 = 200oF = 200 + 460 = 660oR
min

The Enthalpies of Different species at these temperatures have to be obtained by

Case 2:
interpolation:
In this case the cooling process is at constant volume (5 liters): Thus we hace to evaluate
FOR N2 at 660oR, 600 → 751.9
∆U .
661 → HN2, 660
85 86
 700 → 1,450 Before proceeding to discuss the contents of these tables let us briefly review some of the
terminology used in steam calculations: Recall that water can exist in solid (ice), liquid and
60 vapour (or steam) phases and that under certain ranges of conditions these three phases
Q H N 2 , 660 o R = (1,450 – 751.9) + 751.9 = 1171 Btu
100 mol will exist in Equilibrium. At a given pressure, liquid water below its boiling or
HO2 , 660oR = 60 (1471 – 758.8) + 758.8 = 1186 Btu saturation temperature is referred to as Unsaturated liquid. Liquid water at its
100 mol boiling point/temperature is referred to a saturated steam. And the vapour
H CO2 ,660 R = 0.6
o
(1914 – 963) + 963 = 1534 Btu heated beyond the boiling point is that referred to as superheated steam.
mol
Superheated steam is usually characterized by a quantity called degree of superheat.
H CO , 660 o R = 0.6 (1451 – 752.4) + 752.4 = 1172 Btu
The degree of superheat is equal to the number of temperature degrees that the steam is
mol
10 aboveits saturation or boiling temperature at the given pressure. In these steam Tables the
HN 2 , 1010 R =
o
(4,285 – 3,565) + 3565 = 3637 Btu
Subscript S usually referres to saturation (e.g TS,PS) subscript referrs to fluid and g referrs
100 mol
to gas(vapour);
H O2 ,1010 o R = 0.1 (4443 – 3680) + 3680 = 3756 Btu
mol Example 3.8
H CO2 , 1010 R = 0.1 (6167 – 5046) + 5046
O
= 5158 Btu
mol
Saturated water at 127oC and 2.5 bar us heated to 204oC and 17 bars. What are ∆Ĥ and
HCO, 1010oR = 0.1 (4304 – 3580) + 3580 = 3652 Btu
mol ∆Û in KJ ?
Kg
( ) ( ) (
∆H = I N 2 H N 2 , 660 − H N 2 ,1010 + I O2 H O2 , 660 − H O2 ,1010 + I CO2 H CO2 ,660 − H CO2 ,1010 ) Solution: From steam Tables

+ I CO (H CO ,660 − H CO ,1010 ) ⎛ KJ ⎞
At 127oC and 2.5 bar h f ⎛⎜ KJ ⎞ = 535, U f ⎜⎜ ⎟⎟ = 535
⎝ Kg ⎟⎠ ⎝ Kg ⎠
∆H = 0.82 (1171 − 3637 ) + 0.073 (1186 − 3756) + 0.092 (1534 − 5158)
Btu ⎛ KJ ⎞
0.015 (1172 – 3652) = -2580.34
1b mol gas At 204oC and 17 bar h f = 872 ⎜⎜ ⎟⎟, U f = 870 KJ
⎝ Kg ⎠ Kg
Btu
∆H = − 2580.34
1b mol of gas
∆Hˆ = 872 − 535 = 337 KJ
Kg

If the above result is compared with – 2616 Btu it can be observed that the ∆Uˆ = 870 − 535 = 335 KJ
1b mol 7 gas Kg
error is approximately 1.4%. Suggesting that the results are reasonably close.
Example 3.9
Calculation of Enthalpy Changes Using Steam Tables
Steam at 10 bars (absolute pressure), 180oC is fed to a turbine at a rate of 2000 Kg/h. The
The most complete and precisely known tabulations of the Enthalpy and internal energy turbine operation is adiabatic (dQ = 0) and the effluent is saturated steam at 1,0 bar.
functions are those of water. This came about not only because water is such an abundant Calculate the work output of the turbine in Kilo walts, neglecting Kinetic and Potential
substance but also because water, especially in its vapour form, has been the prime Energy changes.
working fluid for devices such as steam engines and steam turbines. Precise design of
these devices require accurate values of the state functions (enthalpy, internal Energy, etc) Solution
as well as the equation of state. Extensive and very detailed tabulation of the
thermodynamic properties of liquid water and its vapour form, commonly called steam, can Steam in Steam out
be found in the compilation due to G.F.C. Rogers and Y.R. Mayhew, 4th Edition blackwell Turbine H2
publishers, 1992. H1
Q=0 W

87 88
 Recall the Energy conservation Equation:
The Energy conservation equation suggests that: 0 0
∆H + ∆ K + ∆ P = Q–W
o o
∆U + ∆ K + ∆ P = Q-W ∆P = 0: No height changes
W = 0: No Mechanical movements
∆U = Q − W , Recall that H = U + PV and Q = ∆H + ∆K
o o
dH = du + PdV + VdP (Total derivative of H) ∆H = ∑I
outlet
i Hi - ∑I
inlet
i Hi

Thus for process involving negligible changes in volume and pressure,

then dH = du ∆H = (295 x 2795) - ((120 x 125.7 ) + (175 x 272.0 ))

Q dH = du = Q − W , Since Q = 0 , Then: ∆H = 7.62 x 10 5 kJ

( )
min
−W = dH = m ∗ Hˆ 2 − Hˆ 1
⎛ Neglecting Kinetic ⎞
m2 (V22 − V12 ) ,
1
∆K = V1 ≅ 0 ⎜⎜ ⎟⎟
From steam Tables: (180oC, 10 bars): H1 = 2778 KJ 2 ⎝ Energy of Inlet Streams ⎠
Kg
1
Saturated steam at 1.0 bar: H2 = 2675 KJ ∆K = ms V V2s, Subscripts referrs to steam.
Kg 2
Q − W = (2675 − 2778) KJ
Kg KJ 1h
x 2000 = − 206,000 .
Kg h h 36005 So, we have to evaluate the exit velocity of steam, Vs.
The cross-sectional Area of the pipe = ∏ R 2
⎛ It ispositive indicating that the ⎞
W = 57.2 kw ⎜⎜ ⎟⎟
⎝ work is coming from the Turbine. ⎠ A = 3.14 x (0.03)2 = 2.83 x 10-3 m2 = A
ms∗ ⋅ Vs
Example 3.10 Steam velocity, Vs = , where Vs is the specific volume of steam. From steam
A
Two streams of water are mixed to form the feed to a boiler. Process data are given as Tables at 17 bar, 204.3oC steam has specific volume of 0.1167 m
3

follows: Kg
Feed stream 1: 120 Kg/min at 30oC
/ / in
3
Kg/ m 1 1m M
Feed stream 2: 175 Kg/min at 65oC V2 = 295 x 0.1167 x x = 203
Boiler Pressure: 17 bars (absolute) min/ K/ g 2.83x10 −3 m
/
2
60 S S

KJ ⎧ Kg M 2 ⎫ ⎧ Kg M M ⎫
x 295 x (203) = 6080
1
The existing stream emerges from the boiler through a 6cm inside diameter pipe. Calculate ∆K = ⋅ ⎬ = ⎨ 2 •
2
⎨ ⎬
the required heat input to the boiler in KJ/min. If the emerging stream is saturated at the 2 Min ⎩ Min S 2 ⎭ ⎩ S Min ⎭
boiler pressure. Neglect Kinetic Energies of the liquid inlet streams. hence, Q = ∆H + ∆K = 7.62 x 105 + 6080
Solution: Basis: 1 minute Q = 7.68 x 105 KJ
Min
mchoro

Enthalpies from steam Tables: 3.9 Enthalpy changes for phase Transitions

At 30oC, hf = 125.7 KJ , At 65oC, hf = 272.0 KJ , At 17 bar, 204.3oC, hg = In the previous discussions (see section 3.6) we have observed that the heat capacity
Kg Kg
functions are discontious at the point of phase transitions. The name that is usually given
2795 KJ to the enthalpy changes for these phase transitions is Latent heat changes Latent
Kg
89 90
meaning ”hidden”, in the sense that, a substance (e.g. water) can absorb a large Three methods are discussed here for estimation of ∆Ĥ V . These are:
amount of heat without any noticeable or significant change in temperature.
This absorbed heat is called latent heat. 4. Using the clausius-clapeyron Equation
5. Using the Chen’s Equation
KJ
e.g. Ice (solid H2O) at OoC can absorb ≈ 334 without undergoing temperature or 6. Using the Watson’s Equation
Kg
pressure rise. Similarly liquid water at 1 atmosphere can absorb ≈ 2256
KJ
before Clausius-Clapeyron Equation:
Kg
temperature and pressure will change. The various enthalpy changes of this kind are The equation can be presented as follows:
termed as follows:
∆Hˆ V ∆Hˆ V
log10 P ∗ = − + B’ or ln (P ∗) = - + B’ (3.16)
Phase Change Enthalpy change 2.303 RT RT
Solid to liquid Latent heat of fussion
Liquid to vapour Latent heat of vapourisation where B’ is a constant that varies from one substance to another P* = vapour pressure, T =
Vapour to liquid Latent heat of condersation
absolute temperature, ∆Ĥ V = Motor latent heat of vapourisation at T, R = Universal gas
Solid to vapour Latent heat of sublimation
constant. From this equation it is apparent that a plot of ln (P*) Versus I will give a
T
The latent heats for the various phase changes can easily be depicted if on an enthalpy
∆Hˆ V
change – Temperature profile as that indicated below: straight line of which the slope will be - and the y intercept will give B’.
R
Mchoro
The values of ln (P*) can be evaluated using the well-known Antonie equation: i.e.
The various types of latent heats of pure substances are usually tabulated in literature. The
symbols that are normally used for latent heats are ∆Ĥ , L, λ , Λ , and hfg (in steam tables). B
ln (P*) = A - (3.17)
In the absence of these tabulated values or experimental values. , the following C +T
approximate methods can be used to provide an estimate of the molar latent heats. Note
that latent heats are normally large amounts of Energy. Therefore it is very important to where: P* = Vapour pressure, [mmHg), T = Absolute temperature, [K]
estimate them properly otherwise they can lead to abnomous errors in energy balances.
A,B,C = Are constants which differ from one substance to another. They are normally
tabulated in literature for various substances.
3.9.1 Estimation of Latent heat of fusion
If follows from the Clausius – Clapeyron Equation that if the vapour pressures of a
There is no accurate and simple way of estimating. ∆ Hfusion. However the latent heat of substance at the temperatures T1 and T2 are known (normally in a very small interval of
fusion for many elements and compounds can roughly be estimated using: Temperature) then; ∆Ĥ V can be computed directly without making a plot, i.e.

⎧2 − 3 for Elements ⎛ P *⎞ ∆Hˆ V ⎡1 1⎤

∆Ĥ f ⎪ In ⎜⎜ 1 ⎟⎟ = ⎢ − ⎥ (3.18a)
= Constant = ⎨5 − 7 for Inorganic compunds (3.15) ⎝ P2 * ⎠ R ⎣ 2
T T1⎦
Tf ⎪9 − 11 for Organic compounds
⎩
P1 ∗ ∆Hˆ V ⎡1 1⎤
Or log 10 = ⎢ − ⎥ (3.18b)
where: ∆Ĥ f = Molar Latent heat of fusuion, ⎡Cal ⎤ P2 ∗ 2.303 R ⎣ 2
T T1⎦
⎢⎣ g mol ⎥⎦
Tf = Melting point, [K]
Using Cher’s Equation:

3.9.2 Estimation of Latent heat of Vapourisation

91 92
 ⎡ ⎛T ⎞ ⎤ Let us make T1 = 360K and T2 = 363K such that ∆ T = 3K;
Tb ⎢0.0331 ⎜⎜ b ⎟⎟ + (0.0297 log10 Pc ) − 0.0327 ⎥
Q In (P1 ∗) = 18.5875 -
3626.55
⎣ ⎝ c⎠
T ⎦ = 7.4532, P1 ∗ = 1725.39 mmHg
∆Ĥ V = (3.19) 360 − 34.29
⎛ Tb ⎞
1.07 − ⎜⎜ ⎟⎟
In (P2 ∗) = 18.5875 -
3626.55
⎝ Tc ⎠ = 7.5548, P2 ∗ = 1909.94 mmHg
363 − 34.29
⎡ KJ ⎤
Where: ∆Ĥ V = Latent heat of vapourisation in ⎢ ⎥L
⎣ g mol ⎦ Thus using:
Tb = Normal boiling point in K [K] ⎛ P ∗⎞ ∆Hˆ V ⎡ 1 1⎤ ∆Hˆ V ⎡ 1 1 ⎤
In ⎜⎜ 1 ⎟⎟ = ⎢ − ⎥ = = ⎢ − ⎥
⎝ P2 ∗ ⎠ R ⎣ T2 T1 ⎦ R ⎣ 363 360 ⎦
Pc = Critical pressure in atmospheres [atm]
8.314 x 4426.483 KJ J
Using the Watson’s Equation: ∆Ĥ V = = 36.80 , R = 8.314
1000 gmol gmol K
0.38
∆Hˆ V2 ⎡1 − Tr2 ⎤
0.38
⎡ T − T2 ⎤
= ⎢ ⎥ = ⎢ C ⎥ (3.20) ∆Hˆ V = 36.80
KJ
∆Hˆ V1 ⎣⎢ 1 − Tr1 ⎥⎦ ⎣ TC − T1 ⎦ gmol

Where: ∆Hˆ V2 = Latent heat of vapourisation of pure liquid at T2

∆Hˆ V1 = Latent of vapourisation of pure liquid at T1 d) Chen’s Equation:
Tb
=
337.9
= 0.6584
Tr = Reduced Temperature T/Tc TC 513.2
Tc = Critical Temperature.
337.9 [0.0331 x 0.6584 − 0.0327 + 0.0297 log 78.5]
∆Ĥ V =
Example 3.11 1.07 − 0.6584

The normal boiling point of methanol (CH3OH) is 337.9 and the critical temperature of this
∆Hˆ V = 37.25 KJ
substance is 513.2K. Estimate the heat of vapourisation of methanol at 90oC. (363K). gmol
Using:

d) Clausius – Clapeyron Equation c) Watson Equation:

e) Chen’s Equation 0.38
f) Walton’s Equation ⎡ 513.2 − 363 ⎤ KJ
∆Hˆ V2 = 35.3 ⎢ ⎥ = 33.87
⎣ 513.2 − 337.9 ⎦ gmol
Solution:

DATA for Methanol: It can be noted that the results are within ± 10%.
Tb = 337.9 K; Tc = 513.2 K; Pc = 78.5 atm [from Table D1, Himmelblau’s book, Pg.667],
KJ To this point, we are now well equipped to handle calculations that involve Enthalpy
∆Ĥrap , at Tb = 35.3 [from the same Table]. Also from Appendix G, (Pg. 685).
gmol changes with phase transitions. Remmembering that Enthalpy is a state function, thus
knowledge of the initial and final state will suffice for the actual computation. The path on
The appropriate Antonie Equation for this substance can be writen as which it has been used to arrive at the final state is immaterial (not important) in these
computations.
In (P ∗) = 18.5875 -
3626.55
T − 34.29 Example 3.12
Compute the Enthalpy change of 1Kg of water from ice at 0oC to vapour at 120oC and 100 k
c) Using the Clausius – Clapeyron Equation Pa.
93 94
 If steam Tables are used for calculation of this Enthalpy change, Then:

( )
∆Ĥ Overall = ∆H fusion + h f100 − h f 0 + ∆H Vap + (h g120 − hg100 )
Solution:
∆H = 335 + (419.1 – 0) + 2256.7 + (2707 – 2675)
∆Ĥ Overall = ∆Hˆ fusion at 0o C + ∆Hˆ Liquid 0 →100o C + ∆Hˆ Vapourisation at 100o C + ∆Hˆ Vapour 100→120o C
From steam Tables: ∆H = 3042
Kj
∆H f = 335 J at 0oC and P* = 101.3 k Pa, ∆Ĥ V = 2256.7 J at 100oC (101.3 k Pa) Kg
g g
The heat capacity Equations can be obtained from Table E.1 (David Himmelblau’s book).

⎡ J ⎤ -2 -5
Cp (liquid) = ⎢ ⎥ = 18.296 + 47.212 x 10 Tk – 133.88 x 10 TK
2

⎣ gmol K ⎦

+ 1314.2 x 10-9 TK3 , TK in [K]

CpVapour ⎡ J ⎤ = 33.46 + 0.688 x 10-2 T +0.7604x10-5 T 2 O

⎢⎣ gmol K ⎥⎦ OC C

-9 o
- 3.593 x 10 TOC , TOC in [ C]
3

∫ (18,296 + 47.212 x 10 TK − 133.88 x 10 −5 TK2 + 1314.2 x10 −9 TK3 )

373 dT
−2
Q ∆Hˆ liquid 0o →100o C =
273

1 ⎡
∆Ĥ = ⎢18.296(373 − 273) +
18 ⎣
47.212 x10 −2
2
373 2 − 273 2 −
3
[
133.88 x10 −5
3733 − 2733 ] ( )

1314.2 x10 −9 ⎤
+ (
373 4 − 273 4 ⎥ ) J
g
4 ⎦

∆Hˆ liquid 0→100o C = 418.6 J or 418.59 J

g g

1 ⎡ 120
CpVapour dT ⎤
18 ⎢⎣ ∫100
∆Hˆ Vapour 100−120o C =
⎦⎥
1 ⎡ 0.688 x10 −2 0.7604 x10 −5 3.593 x10 −9 ⎤
⎢33.46 (120 − 100 ) +
18 ⎣
120 2 − 100 2 + ( )
120 3 − 100 3 − ⎥ ( )
2 3 4 ⎦
(120 4
)
− 100 4 = 38.116 J
g

∆Ĥ Overall = 335 + 418.59 + 2256.7 + 38.116 ≈ 3048 J

g

KJ
∆Hˆ Overall = 3048
Kg

95 96