CHEMICAL ENGINEERING DEPARTMENT
Plant Design and Economics
4.2 Energy Balances
Ousman R.
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4.2. FUNDAMENTALS OF ENERGY BALANCE
1 Introduction:
Important aspect of process analysis is the determination of the energy
requirements and temperatures around systems.
As with mass, energy can be considered to be separately conserved.
Differs from that of mass in that energy can be generated (or consumed) in a chemical process.
Material can change form, new molecular species can be formed by chemical reaction, but the total
mass flow into a process unit must be equal to the flow out at the steady state
The same is true of energy, but not of stream enthalpy. The total enthalpy of the outlet streams will not
equal that of the inlet streams if energy is generated or consumed in the process due to heat of
reaction.
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Cont…
Energy can exist in several forms, including chemical energy,
heat, mechanical energy, and electrical energy.
The total energy is conserved, but energy can be transformed
from one kind of energy to another.
In process design, energy balances are made to determine the
energy requirements of the process: the heating, cooling, and
power required.
In plant operation, an energy balance (energy audit) on the plant
will show the pattern of energy use and suggest areas for
conservation and savings.
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First law of thermodynamics for open systems
Generalized conservation of energy equation
Note that the internal energy is often combined with the flow work into a property called the enthalpy, which is
represented by the symbol H^ and defined as
Ĥ, is defined as the combination of internal energy and flow work, the work that is required to move material into and
out of a process:
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Rate of Work
• It is important to note that the rate of work Ẇ consists of both ‘rate of flow’ work and shaft
work: Ẇ =ẆPV+Ẇs
• Rate of flow work, ẆPV
• This work results from the displacement of fluid during flow and is similar to the pressure-
volume work associated with the compression or expansion of a closed system. However, in
the case of an open system (with inlet and outlet streams), the flow of fluid into and out of a
system represents a continual performance of work as upstream fluid “pushes” fluid into the
system entrance and the fluid in the system “pushes” downstream fluid out of the system exit.
• Rate of shaft work, Ẇs
• When the flowing fluid in a system contacts moving parts, work is performed.
• Shaft work is positive when the net work is on the system (such as in a pump, where the
moving parts are driven by external forces and thereby “push” the fluid).
• Conversely, the shaft work has a negative value when the net work is done by the fluid (such
as in a turbine, where the fluid causes the parts to move).
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• Utilizing the above relationships and the fact that PṼ =P/ρ, we obtain the common
form of the conservation of energy equation
• applications of the steady-state energy balance in which there is negligible
change in kinetic and potential energies and no shaft work.
Latent (phase change) heating or cooling
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4.2. CONSERVATION OF ENERGY
• As for material, a general equation can be written for the conservation of energy:
Energy out = Energy in + generation − consumption − accumulation
This is a statement of the first law of thermodynamics.
An energy balance can be written for any process step.
Chemical reaction will evolve energy (exothermic) or consume energy (endothermic).
For steady-state processes the accumulation of both mass and energy will be zero.
4.3. FORMS OF ENERGY (PER UNIT MASS OF MATERIAL)
4.3.1. Potential Energy
o Energy due to position:
Potential energy per unit mass = gz
where
z = height above some arbitrary datum, m;
g = gravitational acceleration (9.81 m/s2).
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Cont’d…
4.3.2. Kinetic Energy:
Energy due to motion:
𝑢2
Kinetic energy per unit mass =
2
where u = velocity, m/s.
4.3.3. Internal Energy:
The energy associated with molecular motion. The temperature T of a material is a
measure of its internal energy U:
U = 𝑓(𝑇)
4.3.4. Work:
Work is done when a force acts through a distance:
𝑙
𝑤= 𝐹𝑑𝑥
0
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Cont’d…
where:
F=force, N;
x and l = distance, m.
Work done on a system by its surroundings is conventionally taken as negative; work
done by the system on the surroundings, as positive.
Where the work arises from a change in pressure or volume:
𝑣2
𝑤= 𝑝𝑑𝑣
𝑣1
where
P = pressure, Pa (N/m2),
v= volume per unit mass, m3/kg.
• In process design, an estimate of the work done in compressing or expanding a gas is
often required.
• A rough estimate can be made by assuming either reversible adiabatic (isentropic) or
isothermal expansion, depending on the nature of the process.
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Cont’d…
• For isothermal expansion (expansion at constant temperature):
𝑃𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• For reversible adiabatic expansion (no heat exchange with the surroundings):
𝑃𝑣𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• Where 𝛾 = ratio of the specific heats, Cp/Cv.
4.3.5. Heat:
Energy is transferred either as heat or work.
A system does not contain ‘‘heat,’’ but the transfer of heat or work to a system changes
its internal energy.
Heat taken in by a system from its surroundings is conventionally taken as positive; that
given out, as negative.
4.3.6. Electrical Energy:
• Electrical and the mechanical forms of energy are included in the work term in an energy
balance.
• Electrical energy will be significant only in energy balances on electrochemical
processes.
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4.4. THE ENERGY BALANCE:
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Cont’d….
Where;
• The suffixes 1 and 2 represent the inlet and outlet points respectively,
• Q - is the heat transferred across the system boundary: positive for heat entering the
system, negative for heat leaving the system,
• W - is the work done by the system: positive for work going from the system to the
surroundings, and negative for work entering the system from the surroundings.
In chemical processes, the kinetic and potential energy terms are usually small compared
with the heat and work terms, and can normally be neglected.
o And the stream Enthalpy can be defined as,
o H (T,P)
• Values for the more common substances have been determined experimentally and are
given in the various handbooks.
• can be calculated from specific and latent heat data.
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Cont’d…
If the kinetic and potential energy terms are neglected,
This simplified equation is usually sufficient for estimating the heating and
cooling requirements of the various unit operations involved in chemical
processes.
As the flow-dependent terms have been dropped, the simplified equation is
applicable to both static (nonflow) systems and flow systems.
It can be used to estimate the energy requirement for batch processes.
For many processes the work term will be zero, or negligibly small,
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Cont’d…
o Where heat is generated in the system; for example, in a chemical reactor:
Q = Qp + Qs
Qs = heat generated in the system. If heat is evolved (exothermic processes),
Qs is taken as positive, and if heat is absorbed (endothermic processes), it is
taken as negative.
Qp = process heat added to the system to maintain required system
temperature.
Hence:
Qp = H2 - H1 - Qs
H1 = enthalpy of the inlet stream;
H2 = enthalpy of the outlet stream.
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Example 1
Estimate the steam and the cooling water required for the distillation column
shown in the figure.
Steam is available at 25 psig (274 kN/m2 abs), dry saturated.
The rise in cooling water temperature is limited to 30oC.
Column operates at 1 bar.
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Cont’d…
Solution
Material Balance
It is necessary to make a material balance to determine the top and bottoms
product flow rates.
Balance on acetone, acetone loss in bottoms neglected.
1000 ∗ 0.1 = 𝐷 ∗ 0.99
Distillate, 𝐷 = 101 𝑘𝑔/ℎ
Bottoms, 𝐵 = 1000 − 101 = 899 𝑘𝑔/ℎ
Energy Balance
The kinetic and potential energy of the process streams will be small and can be
neglected.
.
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Cont’d…
• Take the first system boundary to include the reboiler and condenser
Inputs: Reboiler heat input QB + feed sensible heat HF.
Outputs: Condenser cooling QC + top and bottom product sensible heats HD +
HB.
The heat losses from the system will be small if the column and exchangers are
properly lagged (typically less than 5%) and will be neglected.
Basis 25oC, 1 h.
Heat capacity data, average values.
Acetone: 25oC to 35oC 2.2 kJ/kg K
Water: 25oC to 100oC 4.2 kJ/kg K
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Cont’d..
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Cont’d…
Reflux ratio:
𝐿
𝑅 = = 10
𝐷
𝐿 = 10 ∗ 101 = 1010 𝑘𝑔/ℎ
𝑉 = 𝐿 + 𝐷 = 1111 𝑘𝑔/ℎ
From vapor – liquid equilibrium data:
𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑓 99% 𝑎𝑐𝑒𝑡𝑜𝑛𝑒/𝑤𝑎𝑡𝑒𝑟 = 56.5𝑜𝐶
At steady state:
𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡
𝐻𝑉 = 𝐻𝐷 + 𝐻𝐿 + 𝑄𝐶,
Hence: 𝑄𝐶 = 𝐻𝑉 − 𝐻𝐷 − 𝐻𝐿
Assume complete condensation.
𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟 𝐻𝑉 = 𝑙𝑎𝑡𝑒𝑛𝑡 + 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 ℎ𝑒𝑎𝑡.
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Cont’d…
There are two ways of calculating the specific enthalpy of the vapor at its boiling point:
1. Latent heat of vaporization at the base temperature + sensible heat to heat the vapor to
the boiling point.
2. Latent heat of vaporization at the boiling point + sensible heat to raise liquid to the boiling
point.
Using the second method,
Latent heat acetone at 56.5oC (330 K) = 620 kJ/kg
Water at 56.5oC(330 K) = 2500 kJ/kg
Taking latent heats as additive:
𝐻𝑣 = 𝑉[ 𝑥𝑤 ∗ 𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 + 𝑋𝐴 ∗ 𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑎𝑐𝑒𝑡𝑜𝑛𝑒 + (𝑇𝑏𝑜𝑖𝑙 − Tliquid)*Cp
ace]
𝐻𝑉 = 1111[(0.01 ∗ 2500 + 0.99 ∗ 620) + (56.5 − 25)2.2]
= 786,699 𝑘𝐽/ℎ
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Cont’d…
• The enthalpy of the top product and reflux are zero, as they are both at the base
temperature. Both are liquid, and the reflux will be at the same temperature as the
product,
hence: 𝑄𝐶 = 𝐻𝑉 = 786,699 𝑘𝐽/ℎ (218.5 𝑘𝑊)
• QB is determined from a balance over the complete system
𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡
𝑄𝐵 + 𝐻𝐹 = 𝑄𝐶 + 𝐻𝐷 + 𝐻𝑊
𝐻𝐹 = 𝐹 ∗ 𝐶𝑝 𝑎𝑐𝑒𝑡 (𝑇 − 𝑇𝑏𝑎𝑠𝑒)
𝐻𝐹 = 1000 ∗ 4.00(35 − 25) = 40,000 𝑘𝐽/ℎ
𝐻𝐵 = 899 ∗ 4.2(100 − 25) = 283,185 𝑘𝐽/ℎ
Hence: 𝑄𝐵 = 𝑄𝐶 + 𝐻𝐵 + 𝐻𝐷 − 𝐻𝐹
= 786,699 + 283, 185 + 0 − 40,000
= 1,029,884 𝑘𝐽/ℎ (286.1 𝑘𝑊)
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Cont’d…
QB is supplied by condensing steam.
𝑘𝐽 𝑘𝑁
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 = 2174 𝑎𝑡 274 2
𝑘𝑔 𝑚
1,029,884
𝑆𝑡𝑒𝑎𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = = 473.7𝑘𝑔/ℎ
2174
QC is removed by cooling water with a temperature rise of 30oC
𝑄𝐶 = 𝑤𝑎𝑡𝑒𝑟 𝑓𝑙𝑜𝑤 ∗ 30 ∗ 4.2
786, 699
𝑊𝑎𝑡𝑒𝑟 𝑓𝑙𝑜𝑤 = = 62,44 𝑘𝑔/ℎ
4.2 ∗ 30
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3.5 CALCULATION OF SPECIFIC ENTHALPY
• Tabulated values of enthalpy are available only for the more common materials.
• In the absence of published data, the following expressions can be used to estimate the
specific enthalpy (enthalpy per unit mass).
For pure materials, with no phase change:
…………… (1)
where;
HT = specific enthalpy at temperature T;
Cp = specific heat capacity of the material, constant pressure;
Td = the datum temperature.
• If a phase transition takes place between the specified and datum temperatures, the
latent heat of the phase transition is added to the sensible-heat change calculated by
equation (1)
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Cont’d…
• The sensible-heat calculation is then split into two parts:
………… (2)
Where;
Tp = phase transition temperature;
Cp1= specific heat capacity of first phase, below Tp;
Cp2 = specific heat capacity of second phase, above Tp;
∆HP = the latent heat of the phase change.
• The specific heat at constant pressure will vary with temperature, and to use
equations (1) and (2), values of Cp must be available as a function of temperature.
• For solids and gases, Cp is usually expressed as an empirical power series
equation:
…. 3a
….. 3b
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Cont’d...
• Absolute (K) or relative (OC) temperature scales may be specified when the relationship is
in the form given in equation 3a. For equation 3b absolute temperatures must be used.
Example:
Estimate the specific enthalpy of ethyl alcohol at 1 bar and 200oC, taking the
datum temperature as 0oC.
Cp liquid 0oC 24.65 cal/mol 0oC
100oC 37.96 cal/mol 0oC
𝑂 _2 2 _9 3
𝐶𝑝 𝑔𝑎𝑠 𝑡 𝐶 14.66 + 3.758 ∗ 10 𝑡 − 2.091 ∗ 10_4𝑡 + 4.740 ∗ 10 𝑡 𝑐𝑎𝑙/𝑚𝑜𝑙
Boiling point of ethyl alcohol at 1 bar = 78.4oC.
Latent heat of vaporization = 9.22 kcal/mol.
Solution:
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Cont’d..
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4.6. MEAN HEAT CAPACITIES
• The use of mean heat capacities often facilitates the calculation of sensible-heat changes; mean heat
capacity over the temperature range t1 to t2 is defined
𝑡2 𝑡2
𝐶𝑝𝑚 𝑑𝑇 = 𝐶𝑝𝑑𝑇
𝑡1 𝑡1
• If the values are for unit mass, calculated from some standard reference temperature, tr, then the
change in enthalpy between temperatures t1 and t2 is given by
∆𝐻 = 𝐶𝑝𝑚, 𝑡2 𝑡2 − tr − 𝐶𝑝𝑚, 𝑡1(𝑡1 − tr)
where tris the reference temperature from which the values of Cpmwere calculated.
• If Cpis expressed as a polynomial of the form 𝐶𝑝 = 𝑎 + 𝑏𝑡 + 𝑐𝑡2 + 𝑑𝑡3, then the integrated form of
𝑡2 𝑡2
equation 𝐶𝑝𝑚 𝑑𝑇 = 𝐶 𝑑𝑇 is,
𝑡1 𝑡1 𝑝
𝑏 2 𝑐 𝑑
𝑎 𝑡 − 𝑡𝑟 + 𝑡 − 𝑡𝑟2 + 𝑡3 − 𝑡𝑟3 + (𝑡4 − 𝑡𝑟4)
𝐶𝑝𝑚 = 2 3 4
𝑡 − 𝑡𝑟
where t is the temperature at which Cpm is required.
• If the reference temperature is taken at 0oC, the above equation reduces to
𝑏𝑡 𝑐𝑡2 𝑑𝑡3
𝐶𝑝𝑚 = 𝑎 + + +
2 3 4
and the enthalpy change from t1 to t2becomes ∆𝐻 = 𝐶𝑝𝑚, 𝑡2 𝑡2 − 𝐶𝑝𝑚, , 𝑡1 𝑡1
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4.8. ENTHALPY OF MIXTURES
• For gases, the heats of mixing are usually negligible, and the heat capacities and enthalpies can
be taken as additive without introducing any significant error into design calculations,
𝐶𝑝 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 𝑥𝑎𝐶𝑝𝑎 + 𝑥𝑏𝐶𝑝𝑏 + 𝑥𝑐𝐶𝑝𝑐+ . . .
where xa, xb, xc, etc., are the mole fractions of the components a, b, c (or weight
fractions if the specific heat per unit mass is used).
• For mixtures of liquids and for solutions, the heat of mixing (heat of solution) may
be significant, and so must be included when calculating the enthalpy of the mixture.
• For binary mixtures, the specific enthalpy of the mixture at temperature t is given by
𝐻 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 , 𝑡 = 𝑥𝑎𝐻𝑎, 𝑡 + 𝑥𝑏𝐻𝑏, 𝑡 + 𝑥𝑐∆𝐻𝑚, 𝑡
• where 𝐻𝑎 and 𝐻𝑏, 𝑡 are the specific enthalpies of the components a and b and ∆𝐻𝑚, 𝑡
,𝑡
is the heat of mixing when 1 mol of solution is formed, at temperature t.
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4.9. HEATS OF REACTION
• If a process involves chemical reaction, heat will normally have to be added or removed.
• The amount of heat given out in a chemical reaction depends on the conditions under
which the reaction is carried out.
• The standard heat of reaction is the heat released when the reaction is carried out under
standard conditions: pure components, pressure 1 atm (1.01325 bar) and temperature
usually, but not necessarily, 25oC.
• Values for the standard heats of reactions are given in the literature or can be calculated.
• It is usually more convenient to express the heat of reaction in terms of the moles of
product produced, for the conditions under which the reaction is carried out, kJ/mol
product.
• Standard heats of reaction can be converted to other reaction temperatures by making a
heat balance over a hypothetical process, in which the reactants are brought to the
standard temperature, the reaction carried out, and the products then brought to the
required reaction temperature as follows in the fig ,
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Cont’d…
Fig. ∆𝐻𝑟 at temperature t.
∆𝐻𝑟, 𝑡 = ∆𝐻𝑜𝑟 + ∆𝐻𝑃𝑟𝑜𝑑 − ∆𝐻𝑟𝑒𝑎𝑐𝑡
Where - ∆𝐻𝑜𝑟 is the standard heat of reaction per mol of the particular product.
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Cont’d…
where
−∆𝐻𝑟, 𝑡 = heat of reaction at temperature t;
∆𝐻𝑟𝑒𝑎𝑐𝑡. = enthalpy change to bring reactants to standard temperature;
∆𝐻𝑃𝑟𝑜𝑑 .= enthalpy change to bring products to reaction temperature, t.
• For a practical reactor, the heat added (or removed) Qp to maintain the design reactor
temperature will be given by
𝑄𝑝 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 – 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 – 𝑄𝑟
where
𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 is the total enthalpy of the product streams, including unreacted materials
and byproducts, evaluated from a datum temperature of 25oC;
𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 is the total enthalpy of the feed streams, including excess reagent and inerts,
evaluated from a datum of 25oC;
𝑄𝑟is the total heat generated by the reactions taking place, evaluated from the standard
heats of reaction at 25oC (298 K)
𝑄𝑟 = −∆𝐻𝑜𝑟 ∗ (mol of product formed)
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4.9. STANDARD HEATS OF FORMATION
• The standard enthalpy of formation ∆𝐻𝑜𝑓 of a compound is defined as the enthalpy
change when one mole of the compound is formed from its constituent elements in the
standard state.
• The enthalpy of formation of the elements is taken as zero.
• The standard heat of any reaction can be calculated from the heats of formation −∆𝐻𝑜𝑓 of
the products and reactants, if these are available or can be estimated.
• Conversely, the heats of formation of a compound can be calculated from the heats of
reaction, for use in calculating the standard heat of reaction for other reactions.
∆𝐻𝑜𝑟 = ∆𝐻𝑜𝑓 , product − ∆𝐻𝑜𝑓 , reactants
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Cont’d…
Example:
Calculate the standard heat of the following reaction, given the enthalpies of formation:
4𝑁𝐻3(𝑔) + 5𝑂2(𝑔) = 4𝑁𝑂(𝑔) + 6𝐻2𝑂(𝑔)
Standard enthalpies of formation kJ/mol
NH3(g) - 46.2
NO(g) +90.3
H2O(g) -241.6
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4.10. HEATS OF COMBUSTION
• The heat of combustion of a compound ∆𝐻𝑜𝑐 is the standard heat of reaction for complete
combustion of the compound with oxygen.
• The general expression for the calculation of heats of reaction from heats of combustion
is
∆𝐻𝑜𝑟 = ∆𝐻𝑜𝑐 , reactants − ∆𝐻𝑜𝑐 , products
4.11. COMPRESSION AND EXPANSION OF GASES
• The work term in an energy balance is significant when a gas is expanded or
compressed as part of the process.
𝑣2
−𝑤 = 𝑝𝑑𝑣
𝑣1
• To compute the pressure work terma relationship between pressure and volume during
the expansion is needed.
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Cont’d…
• If the compression or expansion is isothermal (at constant temperature), then for unit
mass of an ideal gas;
𝑝𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑝2 𝑅𝑇1 𝑝
and the work done, −𝑤 = 𝑝1𝑣1 ln = ln( 2)
𝑝1 𝑀𝑤 𝑝1
where
P1=initial pressure;
P2=final pressure;
v1 =initial volume;
Mw=molecular mass (weight) of gas.
• In industrial compressors or expanders the compression or expansion path will be
‘‘polytropic,’’ approximated by the expression:
𝑝𝑣𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
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Cont’d…
• The work produced (or required) is given by the general expression:
where
Z = compressibility factor (1 for an ideal gas);
R =universal gas constant, 8.314 J/Kmol;
T1 = inlet temperature, K;
W =work done, J/kg.
The value of n will depend on the design and operation of the machine .
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4.12. Electrical Drives
•
