Energy Balance

 Energy conservation principle, similar to the

conservation of mass can be written as:
1. Macroscopic energy balance
2. Microscopic energy balance
 Conservation equation:
Rate of energy 
Rate of energy  Rate of energy   
   generation 
into the system  out of the system  in the system 
 
Rate of change of work 
  Rate of change 
 between the system and   
the surroundings  of energy in the system 
 

Mathematical Modeling in Chemical Engineering

 Macroscopic Energy Balance
2

Example 1
Let us consider the continuous stirred-tank reactor
(CSTR) but this time, there is a cooling coil inside the
reactor, so that the heat released during the course of
the exothermic reaction can be removed.
F0
ρ0
T0
CB0

k
B D
l Q
QG
F
V ρ T CB ρ
T
CB
Mathematical Modeling in Chemical Engineering
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Assumptions:
• Reactor is perfectly-mixed
• Reaction rate is rB = -kCB
• Reactor walls are well insulated
• Only effects of Ei, Ek, and Ep are considered;
other energies are ignored.
We know that:
Heat of reaction is l (kJ/mole reacted B).
Rate of heat generation due to reaction is
proportional to rate of consumption of B:
QG = l (V k CB)

Mathematical Modeling in Chemical Engineering

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General energy balance for reactor:

F0 0 Ei 0  Ek 0  E p 0   F Ei  Ek  E p   QG  Q   W  FP  F0 P0 
d V Ei  Ek  E p 

dt
Ei : internal energy (energy/unit mass)
Ek : kinetic energy (energy/unit mass)
Ep : potential energy (energy/unit mass)
W : shaft work done by the system (energy/time)
P : pressure of the system
P0 : pressure of the feed stream
QG : heat generated inside the system (energy/time)
Q : heat removed from system by cooling coil (energy/time)

Mathematical Modeling in Chemical Engineering

 5
In this system:
• There is no shaft work, so W = 0.
• If inlet and outlet flow velocities are not very high, kinetic
energy terms can be neglected.
• If distance between elevations of inlet and outlet streams is
small, then potential energy term can be neglected.

d VE i 
 F0  0 E i 0  FE i   QG  Q   FP   /    F0 P0 (  0 /  0 )
dt
 = 1/ (m3/kg) is the specific volume

d VE i 
 F0  0 E i 0  FE i   QG  Q   FP  F0 P0  0 0 
dt
Mathematical Modeling in Chemical Engineering
 6

dVEi 
 F00Ei0  FEi   QG  Q   FP  F0P00  0 
dt
 F00 Ei0  P0  0   FEi  P   QG  Q 

We know that H  Ei  P and QG  (rB V )l

Thus, the above equation becomes
dVEi 
 F00H0  FH  Q  rB V l
dt
For liquids, P  Ei, thus we can ignore the term P.
H  Ei  P  Ei
dVH
 F00H0  FH  Q  rB V l
dt
Mathematical Modeling in Chemical Engineering
 7

The heat capacity at constant pressure (Cp) and at

constant volume (Cv) are
 dH   dEi 
CP    CV   
 dT P  dT  V
For incompressible fluids, H  CpT .
dVCP T 
 F00H0  FH  Q  rB V l
dt
Assume that densities and heat capacities of all
liquid streams are constant:
 dVT  
CP    F00H0  FH  Q  rB V l
 dt 
Mathematical Modeling in Chemical Engineering
 Example 2
8

Change of Temperature of a Liquid in a Tank

A perfectly mixed tank of volume V is filled with a
liquid of density . The tank is heated with a hot oil
stream circulated through a coil in its walls. The
rest of the tank wall is well-insulated.
Derive an equation defining the change of the
temperature of the liquid with time after starting of
the hot oil flow.

Mathematical Modeling in Chemical Engineering

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Hot oil
V
ρ

Assumptions:
• Tank is an adiabatic system
• The properties of fluid are constant
• Effects of all energies, except internal, negligible

Mathematical Modeling in Chemical Engineering

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What type of system? Macroscopic System

Macroscopic energy balance for the tank is :

d( VE i )
0  0  UATw  T  
dt
U = overall heat transfer coefficient of tank walls
Tw = temperature of tank walls
T = temperature of liquid
A = heat transfer area of coil

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For incompressible fluids: Ei  H = CPT

If Cp and  are constant, then equation becomes:
dT
UA Tw  T   VCP
dt
Solve by “separation of variables”:
VCP dT dT
dt  a
UA Tw  T  Tw  T 
VCP
where a 
UA
Integration gives: t  a lnTw  T   C
Mathematical Modeling in Chemical Engineering
 12

Initial Condition: T=T0 @ t=0

0  a lnTw  T0   C  C  a lnTw  T0 

t  -a lnTw  T   a lnTw  T0 

Tw  T   e UA / VC P t

Tw  T0 
T  Tw  Tw  T0 e  UA / VCP t

Mathematical Modeling in Chemical Engineering

 Microscopic Energy Balance
13

Microscopic energy balance, similar to the microscopic

mass balance, is applied to microscopic systems such as
tubular reactors, heat exchangers, various fluids and
solid systems.
A typical example of energy conservation application on
microscopic scale is the heat diffusion equation, which
defines the temperature distribution in a solid continuum
as a function of position in three dimensions in the
rectangular coordinates (x, y, z).
This equation is obtained by applying the conduction
energy balance over a solid slab in rectangular
coordinates.
Similarly, the heat diffusion equation can also be driven
for cylindrical and spherical coordinates.
Mathematical Modeling in Chemical Engineering
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• Consider solid slab of three dimensions

• Choose “volume element”: x y z
• Write conduction heat balance over it
• Begin by considering conduction heat fluxes
entering and leaving faces perpendicular to x-, y- & z- axis
• These flux terms are designated as qx, qy ve qz
qy qz
y  y z  z
z

qx qx x  x
x Control
volume z
y
y

x
qz qy
y
x
z

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 15

Conduction heat balance for the control volume:

x direction :
Energy entering at x = x : yzqxx
Energy leaving at x = x+x : yzqxx + x
Similar expressions may be also written for other faces.
Rate of energy generation within CV : xyzqG
Rate of energy change within CV : (xyzEi)/t
The energy balance then becomes :
 
yz q x x  q x x  x  xz q y y  q y y y  xy q z z  q z z  z  xyz q G
E i
 xyz 
t
Mathematical Modeling in Chemical Engineering
 16

By considering that for solids, H  Ei = CpT, and dividing the

entire equation with xyz we obtain

q x x  qx x  x
 q y y  qy
y  y
  q z z  qz z  z
 q 
H
x y z t
G

Taking the limits as x, y and z  0, we get

 qx qy qz  T

     qG  CP
 x y z  t
The conduction heat flux may be evaluated from Fourier’s Law

T T T
qx  k qy  k qz  k
x y z
Mathematical Modeling in Chemical Engineering
 17

Heat diffusion equation in  T   T   T  qG  CP T

2 2 2

rectangular coordinates x 2 y 2 z 2 k k t

From its solution, we obtain temperature distribution as

function of time and position in three directions
T = f(x, y, z, t)

We may write this equation more conveniently in

vector symbolism by using Nabla (divergence)
operator:
CP T
k t
  2 .T (for no heat generation) 
Mathematical Modeling in Chemical Engineering
 Example 3
18

Energy balance for a tubular reactor

Consider a tubular reactor, in which a first order exothermic
chemical reaction (A  B) is taking place. We assume that,
there are no radial temperature, velocity or density gradients.
Temperature of the mixture in the reactor, however, is
changing with the axial position. The reactor has a cooling
jacket through which water is circulated. Heat can be
transferred from the process fluid consisting of reactants and
products at temperature T to the walls of the reactor at
temperature Tw and from walls to the cooling water.

We want to derive a mathematical equation, which describes

the temperature distribution along the axial direction of the
reactor.

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 19

For complete description of system energy balance for process

fluid:
Properties of metal walls and cooling water must be established.
In this problem we will restrict our concern to process fluid only.
Cold water
Tw Assumptions:
• Potential energy and kinetic
energy terms assumed to be
CA0 CA
T0 (t)
u(t,x)
T negligible
• Diffusional mass flow negligible
compared to bulk flow
• No work involved
Hot water

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 20

Energy balance for control volume Ax:

1 2 1. Energy in by bulk flow at x=x: uACp(T -T0)x
2. Energy out by bulk flow at x=x+x: uACp(T-T0)x+x
5 3. Conduction heat flow in at x=x: Aqxx
3 4 4. Conduction heat flow out at x=x x: Aqxx+x
5. Heat generated by chemical reaction: l(kRCA)Ax
6. Heat transferred to the metal wall: U(Dx)(T – Tw)
6 Rate of change of Ei of CV: (AxCp(T-T0))/t
A = cross-sectional area of the reactor (m2)
u = superficial fluid velocity (m/s)
U = overall heat transfer coefficient (kJ/m2.h.oC)
qx = conduction heat flux in x-direction (kJ/m2.s)
kR = reaction rate coefficient (1/s)
T0 = reference temperature (oC)
TD = temperature of inlet water flow (oC)
Tw = temperature of reactor wall (oC)
Mathematical Modeling in Chemical Engineering
 21

By introducing these terms into energy balance equation we get:

uAC T  T 
P 0 x  uACP T  T0  x  x   Aqx x  Aqx  x 
AxCPT  T0 
 k RC A Ax l - UDx T  Tw  
t
Dividing the entire equation by Ax and taking the limit as x  0,
this equation becomes
uCp T  T0  qx UDT  Tw  Cp T  T0 
   (k RC A )l  
x x A t
Right hand-side represents the rate of change of internal energy
of the system. Reaction heat term, (kRCA)l, is positive since it is
considered to be an inflow energy term according to the sign
convention.
Mathematical Modeling in Chemical Engineering
 22

T  T0  T
Since T0 is constant: 
t t
Assuming that k,  and Cp are constant and by introducing
D 2
A
4
T
q x  k Fourier’s Law
x
We obtain the unsteady-state temperature distribution of
the reactor as a function of the axial position:

 2 T uCp T (k RC A )l 4UT  Tw  Cp T

   
x 2
k x k kD k t
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 23

At steady-state:

 2 T uCp T (k RC A )l 4UT  Tw 
   0
x 2
k x k kD

Note that equation contains concentration term (CA)

Thus, for solution we also need:
- total mass balance
- component mass balance

Mathematical Modeling in Chemical Engineering

 Example 4
24

Heating liquid in tank with changing heating surface area

A perfectly mixed cylindrical tank of 30 m3 volume with a single feed
stream is provided with a spiral coil-type heating element in order to
keep the temperature of the water in the tank at a desired level. The
energy needed for heating of content is provided by steam flowing
through the heating element. Heat is transferred to the content in such
way that the area available for the heat transfer (the activated area of
the heating element) is linearly proportional to the quantity of the
liquid in the tank. The heating element is a pipe of 2.5 cm diameter. The
heating coil consists of 10 turns, each having 1mm diameter. The tank is
initially empty. Then water at 20oC is fed into the tank with at a rate of
10 kg/min at t = 0. The temperature of the steam flowing through the
heating element is 105oC. The overall heat transfer coefficient of the
heating element is U = 600 J/m2sK.
Derive a mathematical equation, which can define the change of
temperature of the water with time and calculate the temperature of
the liquid when the tank is filled.
Mathematical Modeling in Chemical Engineering
 25
w
r
T1

Steam (TS =105°C)

Assumptions:
• Temperature of the steam is constant
• Properties of water are constant
• Water is incompressible (Cp =Cv)
• Overall heat transfer coefficient is constant
• Tank is perfectly mixed
• Tank is well insulated (adiabatic system)
• Effects of kinetic and potential energies are negligible
Mathematical Modeling in Chemical Engineering
 26

Let us define following variables for formulation of problem:

A0 = total heat transfer surface area (m2)
At = active heat transfer surface area at time t (m2)
V0 = total volume of the tank (m3)
Vt = volume of the water in the tank at time t (m3)
T = temperature of the water in the tank at time t (K)
T1 = temperature of inlet water flow (K)
T0 = temperature of the water when tank is full (K)
TS = temperature of the steam (K)
Uo = overall heat transfer coefficient of the heating spiral
coil (kJ/m2sK )
t = time elapsed since the starting of water flow (s)
t0 = time needed to fill the tank (t0 =V0/W) (s)
Cp = heat capacity of water (kJ/kgK)
 = density of water (kg/m3)
w = mass flow rate of the feed stream (kg/s)
Mathematical Modeling in Chemical Engineering
 27

System: Liquid in tank at any time

Apply energy (heat) conservation law to water in tank at time t :

F  (E
1 1 i1    
 E k1  E p1 )  F E i  E k  E p  Q G  Q   W  FP  F1P1 
d
 
 Vt  E i  E k  E p
dt

Further assumptions:
• Kinetic & potential energies can be neglected  Ek, Ep = 0
• Shaft work can be neglected  W= 0
• No outlet stream  F=0
• No energy generation in tank  QG = 0
dVtρEi 
 F1ρ1Ei1  F1P1  Q  F1ρEi1  P1ν   Q
dt
Mathematical Modeling in Chemical Engineering
 28

dVtρEi 
 F1ρ1Ei1  F1P1  Q  F1ρEi1  P1ν   Q
dt
dVtρEi 
 FρH1  Q  wH1  Q
dt
Choose temperature of inlet stream (T1) as reference temperature:
H1  Cp (T1  Tref )  Cp (T1  T1 )  0
Ei  Cv (T  T1 )  Cp (T  T1 ) (incompressible fluid)

dVtρCp (T  T1 )
Q
dt
dVtρCp (T  T1 )
Q  U0 A t (Ts  T)   U0 A t (Ts  T )
dt
Mathematical Modeling in Chemical Engineering
 29

Volume of water in tank at any time:

wt
V( t )  wt  V(t) 


Active heat transfer area is proportional to amount of water

in tank:
A( t ) A0
  cons tan t
V( t ) V0

A0 A 0 wt wt
A( t )  V( t )   A(t)  A0
V0 V0  V0

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d   wt    wt 
 Cp (T  T1 )  U0   A 0 (Ts  T )
dt       V0 
d(T  T1 ) wtA 0U0
wCp (T  T1 )  wCp t  (Ts  T )
dt V0
• Introducing dimensionless quantities,
• Converting above ODE into simpler form can facilitate solution
(T  T1 )
 dimensionl ess temperatu re
(Ts  T1 )
t t wt
   dimensionl ess time
t 0 ρV0 /w ρV0
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 31

 d   A 0U0 
     (1  )

 d   wCp  

A 0U0  d 
Define N     N(1  )  
wCp  d 
More simplification is possible by introducing a new parameter
d d
  N d  Nd N
d d
Initial Condition:
d  1 
  1    1 T = T1 @t=0
d    =0 @=0
=0 @=0
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This is a first order homogeneous ODE and may be solved by

“integrating factor (R) method”.
   1  1 
     C  
    e 
Determine the constant using the initial condition  C = 1

   1  1 
       
    e 
The temperature of the liquid when the tank is filled:

T0  T1 1  exp( U0 A 0 / wCp )

 1
Ts  T1 (U0 A 0 / wCp )
Mathematical Modeling in Chemical Engineering