Energy Balances

Lecture Five
 Introduction
 Process industries have always recognized that wasting energy
leads to reduced profits.
 As an engineer designing a process, one of your principal jobs
would be to account carefully for the energy that flows into and out
of each process unit and to determine the overall energy
requirement for the process.
 In process design, energy balances are made to determine the
energy requirements of the process: the heating, cooling, and power
required.
 Conservation of energy
Energy out = Energy in + generation - consumption - accumulation

This is a statement of the first law of thermodynamics.

 Chemical reaction will evolve energy (exothermic) or consume
energy (endothermic). For steady-state processes the accumulation
of both mass and energy will be zero.
 Energy can exist in many forms and this, to some extent, makes an
energy balance more complex than a material balance.
 
Forms of energy (per unit mass of material)
Energy is often categorized as:
1. Potential Energy
Energy due to position: Potential energy per unit mass = gz
where z = height above some arbitrary datum, m;
g = gravitational acceleration
2. Kinetic Energy
Energy due to motion: Kinetic energy per unit mass =
where u = velocity, m/s.
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. Work
Work is done when a force acts through a distance:

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:

 where P = pressure, Pa (N/), v = volume per unit mass, /kg.

 To integrate this function, the relationship between pressure and
volume must be known.
 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.
 For isothermal expansion (expansion at constant temperature):
Pv = constant
 For reversible adiabatic expansion (no heat exchange with the
surroundings):

 Where, = ratio of the specific heats, /

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.
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.
 The Energy balance

 Consider a steady-state process represented by Figure below. The

conservation equation can be written to include the various forms
of energy.
For unit mass of material:
..... (1)

 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.
 It is convenient, and useful, to take the terms U and Pv together;
defining the term enthalpy, usual symbol H, as:
H = U + Pv
 Enthalpy is a function of temperature and pressure.
 Enthalpy can be calculated from specific and latent heat data.
 If the kinetic and potential energy terms are neglected equation (1)
simplifies to: ………. (2)
 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
(non-flow) 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,
and equation (2) reduces to the simple heat balance equation:
…….. (3)

 Where heat is generated in the system; for example, in a chemical

reactor: ………. (4)
 
= heat generated in the system. If heat is evolved (exothermic
processes) is taken as positive, and if heat is absorbed (endothermic
processes) it is taken as negative.
= process heat added to the system to maintain required system
temperature. Hence:
…….. (5)
 = Enthalpy of the inlet stream, = Enthalpy of the outlet stream.
 Energy balances on closed systems

 A system is termed or according to whether or not mass crosses the

system boundary during the period of time covered by the energy
balance.
 A batch process system is, by definition, closed, and semibatch and
continuous systems are open.
 An integral energy balance may be derived for a closed system
between two instants of time. Since energy can neither be created
nor destroyed, the generation and consumption terms of the general
balance drop out, leaving
Accumulation = Input – Output …….. (6)
 In deriving the integral mass balance for a closed system we
eliminated the input and output terms, since by definition no mass
crosses the boundaries of a closed system.
 It is possible, however, for energy to be transferred across the
boundaries as heat or work, so that the right side of Equation (6)
may not be eliminated automatically.
 As with mass balances, however, the accumulation term equals the
final value of the balanced quantity (in this case, the system energy)
minus the initial value of this quantity. Equation (6) may therefore
be written
…….. (7)
 Now

 
where the subscripts i and f refer to the initial and final states of the
system and U, , , Q, and represent internal energy, kinetic energy,
potential energy, heat transferred to the system from its surroundings,
and work done by the system on its surroundings. Equation (7) then
becomes:
…….. (8)

…….. (9)
 
 Equation (9) is the basic form of the first law of thermodynamics
for a closed system. When applying this equation to a given process,
you should be aware of the following points:
1. The internal energy of a system depends almost entirely on the
chemical composition, state of aggregation (solid, liquid, or gas),
and temperature of the system materials. It is independent of
pressure for ideal gases and nearly independent of pressure for
liquids and solids. If no temperature changes, phase changes, or
chemical reactions occur in a closed system and if pressure changes
are less than a few atmospheres, then
2. If a system is not accelerating, then = 0. If a system is not rising or
fall in, then = 0.
3. If a system and its surroundings are at the same temperature or the
system is perfectly insulated, then Q = 0. The process is then termed
adiabatic.
4. Work done on or by a closed system is accomplished by movement
of the system boundary against a resisting force or the passage of an
electrical current or radiation across the system boundary. Examples
of the first type of work are motion of a piston or rotation of a shaft
that projects through the system boundary. If there are no moving
parts or electrical currents or radiation at the system boundary, then
W = 0.
 Energy balances on open systems at steady state

 An open process system by definition has mass crossing its

boundaries as the process occurs. Work must be done on such a
system to push mass in, and work is done on the surroundings by
mass that emerges. Both work terms must be included in the energy
balance.
Flow Work and Shaft Work
 The net rate of work done by an open system on its surroundings
may be written as: …….. (10)
Where,
= shaft work, or rate of work done by the process fluid on a
moving part within the system (e.g., a pump rotor)
= Flow work, or rate of work done by the fluid at the system outlet
minus the rate of work done on the fluid at the system inlet.
 To derive an expression for, we initially consider the single-inlet–
single-outlet system shown here.

…….. (11)
while the fluid leaving the system performs work on the surroundings
at a rate ……………….. (12)
 The net rate at which work is done by the system at the inlet and
outlet is therefore
……………….. (13)
 If several input and output streams enter and leave the system, the
products for each stream must be summed to determine
Specific Properties and Enthalpy

 A specific property is an intensive quantity obtained by dividing

an extensive property (or its flow rate) by the total amount (or flow
rate) of the process material.

……………….. (14)
Similarly, a continuous stream of this material with a mass flow rate
(kg/s) transports internal energy at a rate
……………….. (15)
A property that occurs in the energy balance equation for open systems
is the specific enthalpy defined as
……………….. (16)
Where P is total pressure, and are specific internal energy and
specific volume respectively.
 The Steady-State Open-System Energy Balance

 The first law of thermodynamics for an open system at steady state

has the form
Input = Output ……………….. (17)
 “Input” here signifies the total rate of transport of kinetic energy,
potential energy, and internal energy by all process input streams plus
the rate at which energy is transferred in as heat, and “output” is the
total rate of energy transport by the output streams plus the rate at
which energy is transferred out as work.
 If denotes the total rate of energy transport by the jth input or
output stream of a process, and are again defined as the rates
of flow of heat into and work out of the process, then Equation (17)
may be written:
 ……………….. (18)

If are the flow rates of mass, kinetic energy, potential

energy, and internal energy for the jth process stream, then the total
rate at which energy is transported into or out of the system by this
stream is

……………….. (19)
where is the velocity of the jth stream and is the height of this
stream relative to a reference plane at which
 The total work done by the system on its surroundings equals the
shaft work plus the flow work (10). If is the volumetric flow
rate of the jth stream and is the pressure of this stream as it
crosses the system boundary

……….. (20)
Substituting the expression for of equation (19) and that for of
equation (20) into equation (18) and bringing the terms to the
left side yields.

….. (21)

Equation (21) could be used for all steady-state open system energy
balance problems. As a rule, however, the term is combined
and written as , the variable previously defined as the specific
enthalpy. In terms of this variable, Equation (21) becomes

….. (22)
  Finally, let us use the symbol to denote total output minus total
input, so that,
…..…..(23a)

…….(23b)

…..…..(23c)

 In terms of these quantities, Equation (22) becomes

…..…..(24)

Equation (24) states that the net rate at which energy is transferred to a
system as heat and/or shaft work ( ) equals the difference between
the rates at which the quantity (enthalpy + kinetic energy + potential
energy) is transported into and out of the system ( ).
Notice that if a process has a single input stream and a single output
stream and there is no accumulation of mass in the system
(so that ), the expression for Equation (23a)
simplifies to
….…..…..(25)

Also notice that if a specific variable has the same value for all input
and output streams, the corresponding term of equation (24) drops
out. For example, if is the same for all streams, then from equation
(23a)
….…....(26)

But from a total mass balance the quantity in brackets (which is simply
total mass in minus total mass out) equals zero, and hence, .
Energy balance procedures
 
 A properly drawn and labeled flowchart is essential for the efficient
solution of energy balance problems.
 When labeling the flowchart, be sure to include all of the
information you will need to determine the specific enthalpy of each
stream component, including known temperatures and pressures.
 In addition, show states of aggregation of process materials when
they are not obvious: do not simply write O, for example, but rather
O(s), O(l), or O(v), according to whether water is present as a solid,
a liquid, or a vapor.
 
Example
Saturated steam at 1 atm is discharged from a turbine at a rate of 1150
kg/h. Super heated steam at 300 and 1atm is needed as a feed to a heat
exchanger; to produce it, the turbine discharge stream is mixed with
superheated steam available from a second source at 400 and 1 atm.
The mixing unit operates adiabatically. Calculate the amount of
superheated steam at 300 produced and the required volumetric flow
rate of the 400 steam.
 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:

……….….…....(27)

 
where = specific enthalpy at temperature T,
= specific heat capacity of the material, at constant pressure,
= 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 (27). The sensible-heat
calculation is then split into two parts:

……….….…....(28)

 
Where, = phase transition temperature,
= specific heat capacity first phase, below ,
= specific heat capacity second phase, above .
 
The specific heat at constant pressure will vary with temperature and
to use equations 27 and 28, values of must be available as a function
of temperature. For solids and gases is usually expressed as an
empirical power series equation:
……….….…....(29a)
……….….….....(29b)
Mean heat capacities
 
 The use of mean heat capacities often facilitates the calculation of
sensible-heat changes; mean heat capacity over the temperature
range to is defined by the following equation:

……….….….... (30)
 
 Mean specific heat values are tabulated in various handbooks. If the
values are for unit mass, calculated from some standard reference
temperature, , then the change in enthalpy between temperatures
and is given by:
……….…. (31)
 
where is the reference temperature from which the values of were
calculated.
If is expressed as a polynomial of the form:
then the integrated form of equation (30) will be:

……… (32)

 where t is the temperature at which is required.

 If the reference temperature is taken at 0, equation (32) reduces to:

……… (33)

 and the enthalpy change from to becomes

……… (34)
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), temperature usually, but not necessarily, 25.
 In process design calculations it is usually more convenient to
express the heat of reaction in terms of the mols 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 illustrated in Figure on the next slide.

……… (35)
  Figure. at temperature t
 
Where: = heat of reaction at temperature t,
= enthalpy change to bring reactants to standard temperature, =
enthalpy change to bring products to reaction temperature, t.
 
 For practical reactors, where the reactants and products may well be
at temperatures different from the reaction temperature, it is best to
carry out the heat balance over the actual reactor using the standard
temperature (25) as the datum temperature; the standard heat of
reaction can then be used without correction.
 It must be emphasized that it is unnecessary to correct a heat of
reaction to the reaction temperature for use in a reactor heat-balance
calculation. To do so is to carry out two heat balances, whereas with
a suitable choice of datum only one need be made. For a practical
reactor, the heat added (or removed) to maintain the design reactor
temperature will be given by:
 ……… (36)
 
Where, is the total enthalpy of the product streams, including
unreacted materials and by-products, evaluated from a datum
temperature of 25;
is the total enthalpy of the feed streams, including excess reagent and
inerts, evaluated from a datum of 25;
is the total heat generated by the reactions taking place, evaluated
from the standard heats of reaction at 25 (298 K).
……… (37)
 Where, - is the standard heat of reaction per mol of the particular
product. Note: A negative sign is necessary in equation (37) as is
positive when heat is evolved by the reaction, whereas the standard
enthalpy change will be negative for exothermic reactions. will be
negative when cooling is required.
Effect of pressure on heats of reaction
Equation (35) can be written in a more general form:

……… (38)

 If the effect of pressure is likely to be significant, the change in

enthalpy of the products and reactants, from the standard conditions,
can be evaluated to include both the effects of temperature and
pressure (for example, by using tabulated values of enthalpy) and
the correction made in a similar way to that for temperature only.
 Standard heats of formation
 The standard enthalpy of formation of a compound is defined
as the enthalpy change when one mol 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 - 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.
 The relationship between standard heats of reaction and formation is
given by:
……… (39)
 Heats of combustion
 The heat of combustion of a compound is the standard heat of
reaction for complete combustion of the compound with oxygen.
 Heats of combustion are relatively easy to determine
experimentally.
 The heats of other reactions can be easily calculated from the heats
of combustion of the reactants and products.
 The general expression for the calculation of heats of reaction from
heats of combustion is: ……… (40)

Note: the product and reactant terms are the opposite way round to that
in the expression for the calculation from heats of formation (equation
39).
Mechanical energy balances
 In chemical process units such as reactors, distillation columns,
evaporators, and heat exchangers, shaft work and kinetic and
potential energy changes tend to be negligible compared with heat
flows and internal energy and enthalpy changes.
Energy balances on such units therefore usually omit the former terms
and so take the simple form (closed system) or (open
system).
 Another important class of operations is one for which the opposite
is true heat flows and internal energy changes are secondary in
importance to kinetic and potential energy changes and shaft work.
 Most of these operations involve the flow of fluids to, from, and
between tanks, reservoirs, wells, and process units. Accounting for
energy flows in such processes is most conveniently done with
mechanical energy balance.
 The general form of the mechanical energy balance can be derived
starting with the open system balance and a second equation
expressing the law of conservation of momentum.
 
Consider such a system, letting be the mass flow rate and the
specific volume of the liquid. If is replaced by where is the
liquid density, then the open-system energy balance may be written:

….…....(41)
 The shaft work is the work done by the fluid on moving
elements in the process line.
 In many cases only slight amounts of heat are transferred to or from
the surroundings, there is little change in temperature from inlet to
outlet, and no phase changes or reactions occur. Even under these
circumstances, some kinetic or potential energy is always converted
to thermal energy as a result of friction due to the movement of the
fluid through the system.
 In consequence, the quantity ( ) always has a positive
component, termed the friction loss and is given the symbol .
Equation (41) may therefore be written

….….... (42)
Equation (42) is referred to as the mechanical energy balance. Once
again, it is valid for steady state flow of an incompressible fluid.
A simplified form of the mechanical energy balance is obtained for
friction less processes ( ) in which no shaft work is performed
( ).
….…............ (43)

Equation (43) is called the Bernoulli Equation.

 Process integration and Pinch technology
 Process integration can lead to a substantial reduction in the energy
requirements of a process. In recent years much work has been
done on developing methods for investigating energy integration
and the efficient design of heat exchanger networks.
 One of the most successful and generally useful techniques is that
developed and other workers: pinch technology. The term derives
from the fact that in a plot of the system temperatures versus the
heat transferred, a pinch usually occurs between the hot stream and
cold stream curves.
 It has been shown that the pinch represents a distinct
thermodynamic break in the system and that, for minimum energy
requirements, heat should not be transferred across the pinch,
 
Pinch technology
 The development and application of the method can be illustrated by
considering the problem of integrating the utilization of energy
between 4 process streams. Two hot streams which require cooling,
and two cold streams that have to be heated.
 Each stream starts from a source temperature , and is to be heated or
cooled to a target temperature . The heat capacity of each stream is
shown as CP. For streams where the specific heat capacity can be
taken as constant, and there is no phase change, CP will be given by:

 wherem = mass flow-rate, kg/s

= average specific heat capacity between
Figure. Hot and cold stream composite curves
Significance of the Pinch
 The pinch divides the system into two distinct thermodynamic
regions. The region above the pinch can be considered a heat sink,
with heat flowing into it, from the hot utility, but not out of it.
 Below the pinch the converse is true. Heat flows out of the region to
the cold utility. No heat flows across the pinch.
 If a network is designed that requires heat to flow across the pinch,
then the consumption of the hot and cold utilities will be greater
than the minimum values that could be achieved.
Example
The standard heat of reaction for the oxidation of ammonia is given
below:

 
100 mol /s and 200 mol /s at 25 are fed into a reactor in which the
ammonia is completely consumed. The product gas emerges at 300.
Calculate the rate at which heat must be transferred to or from the
reactor, assuming operation at approximately 1 atm.
Example
A power plant operates as shown in figure on the next slide. Assume
that the pipes, boiler, and superheater are well lagged (insulated), and
that friction can be neglected. Calculate (in Btu/lb steam):
a. The heat supplied to the boiler
b. The heat supplied to the superheater
c. The heat removed in the condenser
d. The work delivered by the turbine
e. The work required by the liquid pumps
Also calculate the efficiency of the entire process defined as

If the water rate to the boiler is 2000lb/hr, what horsepower does the
turbine develop? Finally, what suggestion can you offer that will
improve the efficiency of the power plant?