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2) Mathematical Modeling:

2.1) Introduction:

A chemical plant should operate at a specific steady state condition known as the operating
conditions. However, the plant undergoes dynamics or transient behavior either when the
process is under the influence of disturbances or when the operating condition is changed.

Steady state: means all process variables are stationary, i.e. not changing with time.

Dynamic: means some or all process variables are changing with time.

Hence, since a typical plant undergoes frequent dynamic operation it is necessary to implement
control strategy to restore the steady state operation, i.e. to maintain the plant around its
operating condition.
Mathematical modelling of a process involves developing equations which attempt to describe
the dynamic behaviour of the system/process. These equations are based on the conservation
laws: total mass, component, energy, and momentum.

2.2) Importance of Mathematical Modeling:

 To improve understanding of the process. Models can be analysed to investigate the

behaviour and response to various inputs without unexpected hazards. Behaviour can be
determined before constructing the actual plant. Models can also be used to determine
chemical kinetic mechanisms and parameters from laboratory reaction data. Aids in
scale-up calculations.

 To train operating personnel. Operators can be trained in use of process simulators

which are based on the model of the process.

 To design the control strategy for a new process. The model allows alternate control
strategies to be evaluated.

 To select controller settings. Models may be used to develop appropriate controller

settings prior to start-up of a new process. Studying the effects of and the requirements
for expansion projects. It is easier, cheaper, and safer to conduct studies on a
mathematical model than experimentally on an operating unit.

 To design the control law. Exploring the sizing and arrangement of process equipment for
dynamic performance; studying the interactions of various parts of the process;
simulating start-up and shut-down procedures, and emergency situations and

 To optimise process operating conditions. Allows operating conditions to be adjusted

periodically so that the plant maximises profits and minimises costs.
2.3) Modeling Principles
Conservation Law

 Change in (S) 
 
 within system    All that adds to (S)    All that removes from (S) 
     
time S can be any one time of the following time
 quantities: 

The quantity
 Total Mass 

 Component Mass (Mole)
 Total Energy
 Momentum

2.3.1) Total Material Balances:

Suppose that we have the following physical system:

Water in
Water in


Water out

We represent this system schematically as follows:

Water in 2

1 Pump 3 Tank 4
Water in Water out

Suppose that in the above system x kg/sec of water enters the tank through stream 1 and
y kg/sec through stream 3. How much water is expected to leave through stream 3 ?
(x +y) kg/sec

This is obtained by the law of conservation of mass which states that mass can neither be
created nor destroyed:

 total materialinput   total material output 

  
through system boundary    through system boundary 
or in short:

 time   time  input



     

 0

  
time time

Suppose that a valve is inserted on the downward side of the tank :

Water in

2 Tank 4
Water in Water out

If the valve is closed to some extent, what would happen?

You would have (x + y) kg/sec of water going in and (x + y) – a kg/sec of water leaving.
Where is the remainder of the water?
It accumulates in the tank. accumulation is the rate of change of holdup within the system. It may
be positive (material is increasing), negative (material is decreasing), or zero (steady-state).

Therefore the balance equation (1) becomes:

change inmas of material  toal fowof material into sy tem toal fow of material out of sy tem
   
Several different conventions may be used to denote the flow-rate of a species in a stream:

 withn sy tem    through sy temboundary    through sy temboundary 

The total mass flow-rate is denoted as M
The mass flow-rate of species j is denoted as Mj
The volumetric flow-rate of species j is denoted as Fj

 time   time   time 

Consider each term in the continuity equation:
Term 2:
 total mass input through boundary 

     
 
 time 

 rate of mass flow into system

      
dm j

 M i

Now the fluid would normally enter the system through a conduit of some sort ie via a pipe or a
duct, etc. To obtain an indication of the changing mass flow into the system we can measure the
volumetric flow-rate. Units of volumetric flow-rate: {dV/dt) = [volume/time] = [m3/s].
The volumetric flow-rate is measured by using a rotameter, an orifice plate, a weir, etc.

The units we need are: kg/s

The units we measure are: m3/s

How do we convert from one to the other?

m3 kg kg
s m3 s

Now kg/m3 is the density of the fluid.

 mass flow-rate = volumetric flow-rate  density

 M
i  ρ i Fi
If we cannot measure the volumetric flow-rate of the fluid we may be able to measure the
velocity of the fluid entering the pipe.
The units of velocity are: m s-1

m kg m2 kg
s m3 s

 to convert from velocity to mass, multiply by  A

  M
i   vi ρ A

If the fluid flowing through the pipe is a gas then convert known stream volumes or volumetric
flow-rates to mass or molar quantities, using tabulated densities or gas law. In mass balance
equations, the mass or molar quantities are required. However, in industry it is easier to measure
the volumetric flow-rate using on-line instruments such as rotameters or differential pressure
gauges. We need to convert these volumetric flow-rates to mass or molar flow-rates. We do this
by using the following equation:

mass m
ρ  
volume V

 m  ρV

or n 

For gases, it is easier to measure the pressure, temperature and volumetric flow-rate, than the
mass or moles of gas. To obtain the mass or moles we use the following equation:
We assume that the gas is ideal:

 PV  nRT
 N 
M 
d Mi M W PV

 M   i
dt RT

 M 
 i  W i


Mw = molecular mass of gas

Term 3:

 
total mass output through boundary 

time 

  rate of mass flow out of system



 M o

Analysis of this term is identical to that of term 2:

 M
o  ρ

V o

Term 1:
 
accumulati on of mass within system 

time 

  rate of accumulati on of mass



In order to determine the accumulation of mass of fluid in a container, we need to obtain an

expression for the change in mass of the fluid within the container. It is not normally possible to
measure the change in mass directly. Instead one measures the change in volume of the fluid
within the container. A conversion from volume to mass is therefore required:

The units we need are: kg/s

The units we measure are: m3/s

How do we convert from one to the other?

m3 kg kg
s m3 s

Now kg/m3 is the density of the fluid.

 accumulati on of mass within system  dM d ρ V 

    
 time  dt dt

 substituting the various expression into the total mass balance gives:
d ρV 
 ρ F
i i  ρ F
o o

2.3.2) Component Balance: Introduction:

Unlike total mass, chemical components are not conserved when a chemical reaction occurs –
some species are consumed while others are generated. Before defining the mole balance we
consider a few related terms.

Chemical Species: Any chemical compound or element with a given identity.

Identity: Kind, number, and configuration (spatial arrangement) of the atoms

making up the species.
Chemical Reaction: A chemical reaction is said to occur when a detectable number of
molecules of a species have lost their chemical identity to form a new
Chemical species can lose their identities via one of three ways:

Decomposition:where a molecule is broken down into smaller molecules, atoms,

or atom fragments.
Combination: where one molecule/atom combines with another molecule/ atom.
Isomerization: where a new species is formed simply by the change in
configuration of the atoms making up the species.
Homogeneous Reaction: A reaction that takes place in one phase alone.
Heterogeneous Reaction: A reaction that requires at least 2 phases to proceeds at the rate it
Reactors: A reactor is a vessel in which a chemical reaction occurs.
Irreversible Reaction: a reaction that proceeds only in one direction and continues in that
direction until the reactants are exhausted.
Reversible Reaction: a reaction that can proceed in either direction, depending on the
concentrations of reactants and products relative to their
corresponding equilibrium concentrations. Some Types of Reactors:

Batch Reactor:

In this type of reactor, reactants are initially charged into the reactor and left to react for a certain
period. The resultant mixture is then discharged. This type of reactor results in an unsteady
operation – composition of a particular species changes with time. At any instant the
composition/concentration is uniform throughout the reactor.

Semi-Batch Reactor:


This type of reactor has either an input OR an output stream.

Continuous Reactors

This reactor has both input and output streams. Since the reactor contents is well stirred the
composition of the output stream is equivalent to that of the composition within the reactor. This
type of reactor is also known variously as a continuous stirred tank reactor (CSTR), back mix
reactor (BMR), or mixed flow reactor (MFR). These reactors are normally run at steady-state.

This type of reactor consists of a cylindrical pipe or tube – it is therefore called a tubular reactor.
It is normally operated at steady-state. The flow of fluid through the reactor is smooth – there is
no element of fluid mixing with that before or after it. There is no radial variation in concentration
– element moves through reactor as a plug – therefore also called a plug flow reactor (PFR).
The reactants are continually consumed as they move down the reactor.

Catalytic Reactors:

Fixed Bed Reactors Fluidised Bed Reactor MOLE BALANCES

Rate of Reaction (rj):

Consider the reaction:

aA + bB  cC + dD

The rate of reaction for the above reaction is defined as the number of moles of species A
reacting (disappearing) per unit time per unit base. Since species A is a reactant, its
concentration will decrease with time. The symbol for the rate of reaction is consequently: -rA.
The rate of the above reaction can also be expressed in relation to other species involved in the
reaction – if we consider species D, then the rate of reaction is expressed as the number of
moles of species D formed (generated) per unit time per unit base. Since species D is a product,
its concentration will increase with time. The symbol for the rate of reaction is consequently: r D.

Note: -rA and rD are related by the stoichiometric equation. This will be discussed in more detail
in later sections.

The “base” mentioned above is dependent on the reacting system:- If the system is
homogeneous then the base is considered to be the volume of the reacting fluid. In fluid-solid
systems the base could be one of mass of solid, surface area of solids, or volume of solids.

The rate of reaction is a function of temperature and composition (concentration):

rj = f1(temperature)  f2(composition)
= [kA(T)] [f2(CA, CB, CC, . . . )

where k is referred to as the reaction rate constant.

1) k is not strictly a constant – it depends on the temperature of the reacting system.
This will be discussed in more detail in a later section.
2) The rate expression is an algebraic equation.

Concentration Effects on Reaction Rate:

Before determining the form of the concentration term in a rate expression, we need to define
certain terms.

Elementary and Non-elementary Reactions:

The effect of concentration on the reaction rate is almost always determined experimentally. An
elementary reaction is one for which the rate expression can be obtained directly from the
stoichiometric reaction equation. If we consider the following reaction to be elementary:
aA + bB  cC + dD

then an expression for the rate of reaction could be:

-rA = k CAa CBb wrt species A
-rB = k’ CAa CBb wrt species B
+rC = k’’ CAa CBb wrt species C
+rD = k’’’ CAa CBb wrt species D

A non-elementary reaction is one where there is no relationship between the reaction

stoichiometric equation and the rate expression. Consider the following reaction:
H2 + Br2  2HBr
This reaction is considered non-elementary because its rate expression turns out to be

k C C0.5
rHBr 1 H2 Br
 2
k  HBr
2 C

Molecularity and Order of Reaction:

The molecularity of an elementary reaction refers to the number of atoms, ions, or molecules
involved (colliding) in the rate-limiting step of the reaction. This has been found have values of
one (unimolecular), two (bimolecular) and sometimes three (termolecular).

The order of a reaction refers to the powers to which the concentrations are raised in the rate
expression. For example, consider the following rate expression:
-rA = kA CA CB
This reaction is of order  with respect to component A, and of order  with respect to
component B. The overall order of the reaction is n, where n =  + .

Note: the order of a reaction (both with respect to a component and overall) need not be an

The units for k are dependent on the order of the reaction:

Zero-order: -rA = kA
First-order: -rA = kA CA
Second-order: -rA = kA CA2
Third-order: -rA = kA CA3

Determine the dimensions of kA in each of the above cases.

Temperature Effects on Rates of Reactions

The rate law gives the relationship between reaction rate and concentration:

-rA = k(T) f(CA, CB,. . .)

where k is the reaction rate constant or the specific reaction rate.

k is not truly a constant – it is merely independent of the concentration of the species
involved in the reactor.

k(T) = Ae-E/RT

where A is the pre-exponential factor or frequency factor

E is the activation energy [J/mol; cal/mol]
R is the gas constant [8.314 J/mol K; 1.987 cal/mol K]
T is the absolute temperature [K]

General Mole Balance Equation:

Fj Fj

acumltionfmles molesntrig molesaving molesgnrated molescnumed

      dN j

 N ji

 N jo  Gj  Gj

 withnsyem  sytem  sytemwithnsyemwithnsyem

For a product there is no consumption term and for a reactant there is no generation term.

 time   time   time   time   time 

Consider the generation or production term Gj.

moles moles
Gj    volume  rj V
time time  volume

     
Now rj is the rate of reaction which depends on the concentration. Since the concentration
may not be the same throughout the reactor we divide the reactor into unit volumes and
find the rate of reaction in each unit volume. Then the total generation or consumption is
the sum of the generation or consumption in each of these unit volumes.

     

 Gj   m
r jm  Vm 
 r dV

Therefore the mole balance becomes:

dN j
 
N ji  
N jo 
 r dV

2.3.3) Energy Balance:


Similar to that of mass or matter, the law of conservation of energy states that energy can
neither be created nor destroyed, but can be transformed from one form to another.

The Different forms of Energy

Kinetic Energy, EK

Kinetic energy is the energy a system possesses because of a velocity difference between it and
its surrounding at rest:

F x

m [kg]

Consider a body of mass m acted on by a constant force F that produces a displacement x

parallel to the direction of the force. During this displacement the velocity increases from an
initial velocity vo to a final velocity v.
Force, F  ma
where a  acceleration 

The work done  kinetic energy (E K ) is given by :

2 2 2 2 2

      
du dx 1
F  dx  m  a  dx  m  dx  m  du  m u  du  m u 22  u12
dt dt 2
1 1 1 1 1

If the initial velocity  0 and the final velocity  u then then the kinetic energy is given by;

EK  m u2 [N.m], [J]

EK ˆ 1 2
The specific kinetic energy   E K  u
m 2

Gravitational Potential Energy, EP:

The gravitational potential energy is the energy associated with a certain mass of fluid owing to
its vertical position in the earth’s gravitational field.
Consider an object of mass m whose centre of gravity is thrust vertically upward to a height z 2
above its original level z1 by a vertical force F.

mg Z1

Reference plane (Datum line)


EP 

m g dz  m g z 2  z1   J

The specific potential energy is given by :


P   g z 2  z1 
If z1  0 and z 2  z then E ˆ
P   gz  J/kg

Internal Energy, U

The internal energy is the stored energy a system possesses by virtue of the atomic and
molecular energy of the matter of which it is constituted. The internal energy of a body of gas,
containing a certain quantity of molecules, is the sum of the energies represented by the random
molecular translational motion, their molecular rotational and vibrational bond energies and the
submolecular energies of the orbiting electrons. The potential energy due to the force of
attraction between the molecules also contribute towards the total internal energy. In the case of
liquids and solids the relative contribution of the different energies changes drastically. In solids
there is no rapid random motion of its molecules or atoms but only a slow process of diffusion.
The internal energy is an extensive property since it is proportional to the mass of the system in




The internal energy of a system cannot be measured, but can be calculated from other variables
that can be measured, such as pressure, temperature, and volume. The internal energy per unit

mass is called the specific internal energy (Û) [kJ/kg]. It is a function of both temperature and
Û = Û(T, V)

 Û   Û 
     
dÛ  T  dT   V̂  dV̂
  V̂  T

The specific internal energy of a substance is a strong function of temperature. If the

temperature of a system is changed (with the volume maintained constant), the specific internal
energy changes as follows:

Û Û

T (oC)
The slope of the curve at any temperature is called the specific heat capacity at constant volume
 
Ĉ v ˆ dU
 Cv 

 ˆ
dU  Cv dT


 ˆ
ΔU 
v dT

Work Energy:

There are several types of work that one may consider: Flow Work, Displacement Work, and
Shaft Work.

Work is a form of energy in transition or motion. When a system does work on its surroundings,
it transfers to it a certain quantity of energy. Similarly, when the surroundings do work on a
system, the energy level of the system rises.

Sign convention: Work done by the system is positive

Work done to the system is negative

Flow Work  dWf 

 
 dt 
Flow work is done on a system when an amount of fluid flows through the system’s boundary
(control surface) into the system. Alternately, this is the work done on the fluid at the inlet to the
system – forcing the fluid into the system against the pressure of the system at the inlet:

Flow Pi Pi

If P = pressure [N/m2],
A = cross-sectional area [m2],
M = mass of fluid [kg],
x = distance [m]
M = mass flow rate [kg/s]

Flow work (Wf) = Fx
= P A x
= P V

= P  V M

  P  Vˆ  M

Displacement Work:

Displacement work is the work done whenever a force acts through a distance


The work done is defined by the equation: dW = F dx

where F is the component of the force acting in the direction of the displacement dx.

Consider the compression or expansion of a fluid in a cylinder by the movement of a piston. The
force exerted by the piston of the fluid is equal to the product of the piston area and the pressure
of the fluid. The displacement of the piston is equal to the volume change of the fluid divided by
the area.
 dW  P A d 
or, since A is constant:

dW  P dV


W  P dV

This equation must be integrated if the work for a finite process is required: Shaft Work

The term shaft work is used to indicate work done by or on the fluid flowing through a piece of
equipment and transmitted by a shaft which protrudes from the equipment and which either
rotates or reciprocates. Therefore the term is taken to mean the work done which is
interchanged between the system and the surroundings through the shaft. The equipment may
include centrifugal pumps, turbines, reciprocal compressors, etc.

 dQ 
Heat   [kJ]
 dt 

When a hot object is brought into contact with a cold object, the hot object becomes colder and
the cold object becomes warmer. We can assume that something has been transferred from the
hot object to the cold object – this something is called heat (Q). One important observation about
heat is that it always flows from a higher temperature to a lower one. The rate of heat transfer
from one body to another is proportional to the temperature difference between the bodies – the
temperature difference is the driving force for the transfer of heat.

Heat only exists in transit from one body to another, or between the system and the surrounding.
When energy in the form of heat is added to a body it is stored not as heat but as kinetic and
potential energy of the atoms and molecules making up the body.

Enthalpy (H) [kJ]

In many thermodynamic analyses the sum of the internal energy U and the product of pressure
(P) and volume (V) appears. Because the sum U + PV occurs so frequently it is convenient to
give the combination a name, enthalpy, and a distinct symbol, H.
 H = U + PV
The enthalpy per unit mass is called the specific enthalpy, Ĥand is an intensive property.
H  ˆ  PV
U ˆ

It is a function of both temperature and pressure:

Ĥ = Ĥ( T, P)
 H  ˆ
 ˆ
dH    dT   H  dP
 T   P 
 P  T

The specific enthalpy of a substance is a strong function of temperature. If the temperature of a

system is changed (with the pressure maintained constant), the enthalpy changes as follows:

Ĥ Ĥ

T (oC)

The slope of the curve at any temperature is called the specific heat capacity at constant volume
Ĉ 

 CP 

 ˆ
dH  CP dT


 ˆ
ΔH  ˆ H
1 


It is important to note that one cannot calculate the absolute enthalpy – only changes in enthalpy
or the enthalpy relative to some reference state can be determined:


Ĥref reference
Initial state Final state
of system of system

Change in enthalpy (Ĥ) = enthalpy at final state – enthalpy at initial state

= (Ĥ2 – Ĥref)  (Ĥ1 – Ĥref)
= Ĥ2  Ĥ1

Determination of Enthalpy for Systems not Undergoing Phase Change:

Use of Heat Capacity Equations:

ˆ  C dT
dH P
ˆ 
 H C
P dT

The heat capacity (CP) is usually expressed as a function of temperature:

CP  a  bT  cT 2


 ˆ
ΔH 



 a  bT  cT 2
 dT

 T2 T3 
 
 aT  b  c 

 2 3  T1

 a T2  T1  
 T2
 T1
 
 T2
 T1

Values for the constants a, b, and c are found in various references.

Mean Heat Capacity:

If the temperature range (T2 – T1) is large (> 50 oC) then the above equation is used. If the
temperature range (T2 – T1) is small (< 50 oC) then one can use the mean heat capacity:
ˆ  C ΔT

 ˆ  T  T   ΔHˆ  T   ΔH
ΔH ˆ T 
1 2 2 1

 C 
P T2  T2  Tref   C 
P T1  T1  Tref 

Normally the CP data is available based on some reference temperature Tref.

Enthalpy Changes when there is a Phase Change:

Consider a liquid at some fixed temperature T1 with its upper surface exposed to a gas. The
liquid molecules are held in the liquid phase by various attractive forces. These molecules have
some energy and are in constant. If the temperature of the liquid is increased to some
temperature above T1 then the energy of the molecules will increase. Some molecules will have
gained sufficient energy to overcome the attractive forces and will consequently enter the vapour
phase. This phenomenon is known as vapourisation. The net rate of vapourisation is the
difference between the rate which molecules escape from the liquid phase and the rate at which
vapour molecules collide with the liquid surface are recaptured into the liquid phase.

The vapourising molecules will take with them some energy – the average energy of the liquid
phase will thus be reduced. There is a gain in enthalpy associated with the transition from liquid
to vapour at constant temperature. This enthalpy change is called the latent heat of

The reverse of this process (when vapour molecules lose some energy and enter the liquid
phase) is called condensation and the enthalpy change associated with this process is called the
latent heat of condensation.

A similar consideration applies for the transition from solid to liquid (for example, when ice melts
to form a liquid).

From the above we have the following definitions:

Latent Heat of Fusion: ΔĤfheat required to melt a unit amount of solid at constant T
and P
Latent Heat of Vapourisation: ΔHˆ heat required to vapourise a unit amount of liquid at
constant T and P
Latent Heat of Sublimation: ˆ
ΔHs heat required to vapourise a unit amount of solid at
constant T and P
Latent Heat of Condensation: c
heat loss when a unit amount of vapour condenses to liquid
at constant T and P
 ˆ
ΔH ˆ
ΔH 
ΔĤ Enthalpy
condensation vapourisat ion

ΔH fusion

Temperature (K)

Derivation of the Energy Balance:

Consider the following system:

W T To

Q Vo

Ti i
Vi 
M i
Zi Z Zo

The law of conservation of energy states that energy can neither be created nor destroyed – it

changeine rgy flowofen rgy flowofen rgy

can only be transformed from one form to another. This law is based on physical observations
and is not subject to mathematical proof. In its application to energy transformations on earth,

   
there is no known exceptions. The law of conservation of energy (or continuity equation),
therefore, reduces to:

 withnsy tem    intosy tem    outof sy tem

 accumulati on of energy within system 
 
. . . . (1)

 t im e   t im e   t i m e 
 time 

 rate of accumulati on of energy within system

Consider each of the terms in turn:

     
Term 1: 
d 1 
U  M v  M g z 
dt  2

    
 ˆ 1 2  
 U  2 v  g z  M
  
Term 2:
 flow of energy into system 
 
 time 

 rate of flow of energy into system

ˆ 1 2  dMi dQ
  Ui  v i  g zi  
 2  dt dt

ˆ 1 2  
  Ui  v i  g zi M i  Q
 2 

Term 3:  flow of energy out of system 

 
 time 

 rate of flow of energy out of system

ˆ 1 2  dMo dWT
  Uo  v o  g z o  
 2  dt dt

ˆ 1  
  Uo  v o  g z o Mo 2
 W
Substituting (2), (3), and
 (4)2into (1) gives:


d  ˆ 1 2    1 2   1 
 U  v  gz M   Uˆ i  v i  gzi M i   Uˆ o  v o2  gzo M o  Q  W

dt  2    2   2 

The above equation is true for a single inlet and single outlet. For multiple inlets and multiple
outlets the above equation becomes:

d  ˆ 1 2
dt  2
 
 U  v  gz M
 


1 2
 Ui  v i  gz i M

i 


1 2
 Uo  v o  gz o M


 Q  

M  
In terms of measurable quantities, we know that

The energy balance, therefore, becomes:

d  ˆ 1 2   ˆ 1 2  ˆ 1 2 
 U  v  gz  M 
dt  2  

 Ui  v i  gz i ρ iFi
 2 
   Uo  v o  gz o ρ o Fo
outlets  2 
  W
 Q 

Special Cases:

Steady-State Systems:

Under steady-state conditions accumulation = 0

d  ˆ 1 2 
  U  gz  v  m  0
dt  2  

 and M
The mass flowrates M  can be replaced by their steady - state flowrate
i o

equivalent s : m or n

Therefore, we have:


1 2

 Ui  v i  gzi  mi


1 2

 Uo  v o  gzo  mo

 
Q  
W T  0



1 2

 Ui  v i  gzi  ni


1 2

 Uo  v o  gzo  no

 
Q  
W T  0

Closed Systems:

For closed systems there is no transfer of mass across the system boundary.

 M  0 and 
M  0
i o

The energy balance, therefore, becomes:

d  ˆ 1 2    W

 U  gz  v  M  Q T
dt  2  

If we integrate from some initial time t1 to some final time t2:

 ˆ 1 2   ˆ 1  
 U  gz  2 v  M   U  gz  v 2  M  Q  WT
2   t1
   t2 

For a closed system: Mt2 = Mt1 = M

 [Û + g z + ½ v2]M = Q – W
 U + Ep + EK = Q – W

If there is no change in the kinetic and potential energies we have:

U = Q – W

This is the famous First law of Thermodynamics.

The Energy Balance Equation in terms of Enthalpy

Consider the energy balance diagram.

Flow work is done on the fluid at the system inlet (forcing the fluid into the system against a
system pressure PI). This is negative work and is given by:
ˆ M
 Pi V 
i i

Flow work is also done on the fluid at the system outlet (forcing the fluid out of the system
against an outlet pressure Po). This is positive work and is given by:
ˆ M
 Poi V 
o o

The total flow work is, therefore, given by:

W  ˆ M
Po V   ˆ M
Pi V 
f o o i i

The total work is, therefore, given by:

W  W  W

T S f
The energy balance  ˆ M ˆM 
 WS  Po V o o  Pi Vi i

d  ˆ 1 2    1 2   1 
 U  v  gz M   Uˆ i  v i  gzi M i   Uˆ o  v o2  gzo M o
  W
 Q 
dt  2    2   2 
therefore, becomes:
d  ˆ 1 2   ˆ 1 2  ˆ 1 2    ˆ  ˆ 
 U  v  gz  M   Ui  v i  gz i  Mi   Uo  v o  gz o  Mo  Q  WS  Po Vo Mo  Pi Vi Mi
dt  2    2   2 

d  ˆ 1 2   ˆ ˆ  1 v 2  gz  M
   U
ˆ P V
ˆ 1 2   
 U  v  gz  M   Ui  Pi Vi i i i o o o v o  gz o  Mo  Q  WS
dt  2    2   2 

d  ˆ 1 2   ˆ 1 2  ˆ 1 2   
 U  v  gz  M   Hi  v i  gz i  Mi   Ho  v o  gz o  Mo  Q  WS
dt  2    2   2 
For multiple inlets and multiple outlets:

d  ˆ 1 2   ˆ ˆ  1 v 2  gz  M ˆ ˆ  1 v 2  gz  M
 U  v  gz  M
dt  2  
 
 H i  Pi V

i i

 
i 
 H o  Po V

o o

 W
  Q 

d  ˆ 1 2   ˆ ˆ  1 v 2  gz  ρ F  ˆ ˆ  1 v 2  gz  ρ F  Q
dt  U  2 v  gz  M    H i  Pi Vi
i i i i   H o  Po V o
o o o o
 W

   inlets   outlets  

Mechanical Energy Balance:

Consider an open system having one input and one output stream. Assume the system to be at
steady state and the mass flow rate to be M. Assume further that the liquid is incompressible so

V̂i  V̂o  V̂  1

The equation

d  ˆ 1 2    1 2   1 
 U  v  gz  M   Uˆ i  v i  gz i  Mi   Uˆ o  v o2  gz o  Mo  Q  W

dt  2    2   2 
ˆ 1 2  ˆ 1 2 
0   Hi  v i  gzi  M   Ho  v o  gzo  M  Q  Ws
 2   2 

ˆ ˆ  1 v 2  gz  M ˆ ˆ  1 v 2  gz  M
0   Ui  Pi Vi i i   Uo  Po Vo o o  Q  Ws
 2   2 

0  Uˆ
o -U
ˆ M
i 
 Po  Pi 
  M  g z o  z i  M 
1 2

v o  v i2 M   Q  Ws
 ρ  2

ˆM  ΔP  1
0  ΔU    M  g Δz M  Δv 2 M  Q  Ws
 ρ  2

 M

 ˆ Q  ΔP  1 Ws
0   ΔU       g Δz  Δv 2 
 M  ρ  2 M

Now ΔUˆ  Q M is the friction loss or heat that is generated as a result of friction.

  g Δz   f   s
ρ 2 M
For systems where there is no frictional loss and where there is no shaft work:

ΔP Δ v2
 g Δz   0
ρ 2

This is the Bernoulli’s Equation