CONTROL DE PROCESSOS

CHEMICAL PROCESS CONTROL

Degree in Chemical Engineering

University of Alicante

Juan Javaloyes

2021/2022
 Textbooks
Chemical process control : an introduction to theory and practice
STEPHANOPOULOS, George. (1984)

Process modeling, simulation, and control for chemical engineers
LUYBEN, William L. (1990)

Process Dynamics, Modelling and Control
OGUNNAIKE, Babatunde A. and RAY, Harmon W. (1995)

Process Control: Modeling, Design and Simulation
BEQUETTE, Wayne B. (2003)

Process Dynamics and Control
SEBORG, Dale E. et al. (2003)

Chemical process control [34528] Academic year 2021/22 2
 Course Contents – Block diagram
Motivation

Mathematical Tools
Dynamic modeling of 
chemical processes Ordinary Differential 
Equations

Transfer Functions Input‐Output model
Linearization of nonlinear systems
Deviation variables

Dynamic Behavior of First‐, Second‐ and 
Laplace Transforms
Higher‐Order Systems

Solution of ODEs using 
Stability Analysis of  Design of Feedback  Laplace Transforms
Feedback Systems Controllers

Instrumentation and 
Frequency Response
Control valves

Design of Feedback Controllers by 
Advanced Process Control
Frequency Response

Chemical process control [34528] Academic year 2021/22 3
Development of Mathematical 
Models
(State variables and state equations. The input‐output model. Degrees of Freedom. 
Linearization of nonlinear systems. Deviation variables)
 Learning objectives

 Write basic transient and steady state balances
 Determine the state, input and output variables, and the parameters for 
a particular model
 Transform the state equation model into an input‐output model
 Linearize a set of nonlinear equations to find the state space model

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 5

 Process models

Mathematical model (of chemical processes)
“ a collection of mathematical relationships between process variables which 
purports to describe the behavior of physical system. (B. Ogunnaike, 1995)

Distributed and Lumped models
Most chemical engineering systems have thermal, pressure or component 
concentration gradients in the three dimensions, as well as in time. If we want to 
develop a mathematical model of such systems, we will obtain a set of partial 
differential equations (PDEs)  Distributed Models

If the spatial gradients are ignored (perfect mixing assumption), only time gradients 
are considered. Thus, the process can be described using ordinary differential 
equations (ODEs).  Lumped Models

Lumped models are less rigorous than PDEs, but also more easy to solve and most 
of the times provides reasonable approximations for the real process.

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 6

 State Variables and State Equations for a Chemical Process
To characterize a system and its behavior we need…
1. A set of fundamental dependent quantities whose values describe the natural 
state of a given system.
2. A set of equations in the variables above which describe how the natural state 
of the given system changes with time.
Fundamental quantities State Variables
‐ Mass Concentration, temperature, 
‐ Energy pressure, flow rate, volume …
‐ Momentum
State equations
conservation principle
Conservation principle on the 
fundamental quantities

Balance equations Common states

Overall material balance Total mass, volume, level and pressure for gas phase processes

Component material balances Component compositions

Energy balances Temperatures

Momentum balances Pressures, velocities 

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 7

 Conservation relationships

 accumulation of S   flow of S in the system   flow of S out the system 

   
 time period   time period   time period 
 amount of S generated within the system   famount of S consumed within the system 
   
 time period   time period 
where
S (fundamental quantities) : total mass, mass of individual componetes, total energy, momentum

Material Balance Component Balance
dM d  V  d  nA  d  c AV 
   i Fi    j Fj    c Ai Fi   c A j Fj  rV
dt dt iI jJ dt dt iI iI

Energy Balance

d E d U  K  P 
   i Fi hi    j Fj h j  Q  Ws
dt dt iI iI

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 8

 Conservation relationships
Notation
r  density of the material in the system
ri  density of the material in the ith inlet stream
r j  density of the material in the jth outlet stream
V  total volume of the system
Fi  volumetric flow rate of the ith inlet stream
Fj  volumetric flow rate of the jth outlet stream
nA  number of moles of component A in the system
cA  molar concentration of A in the system
cAi  molar concentration of A in the ith inlet stream
cAj  molar concentration of A in the jth outlet stream
r  reaction rate per unit volume of component A in the system
hi  specific enthalpy of the material in the ith inlet stream
h j  specific enthalpy of the material in the jth outlet stream
U , K , P  internal, kinetic and potential energies of the system
Q  amount of heat exchanged between the system and ist srroundings per unit time
Ws  shaft work exchanged between the system and ist srroundings per unit time

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 9

 Additional elements of the mathematical models

Transport rate equations
Needed to describe the rate of mass, energy and momentum transfer between 
a system and its surroundings

Kinetic rate equations
Needed to describe the rates of chemical reactions taking place in a 
system

Phase equilibria relationships
Needed to describe the equilibrium situations reached in a chemical reaction 
or by two or more phases

Equations of state
Needed to describe the relationship among the intensive variables describing 
the thermodynamic state of a system

Chemical process control [34528] Academic year 2021/22 10
 Theoretical Modeling – List of Examples

System
1 Liquid Surge Tank
1.1 Constant holdup (overflow operation)
1.2 Variable holdup (drain by gravity)
1.3 With pump
2 Stirred Tank Heater
2.1 Constant holdup (overflow operation)
2.2 Variable holdup (drain by gravity)
3 Continuous Stirred Tank Reactor (CSTR)
3.1 Isothermal CSTR with first order reaction (variable holdup)
3.2 Nonisothermal CSTR with first order reaction (variable holdup)
4 Mixing Process
4.1 Variable holdup
5 Tubular Heat Exchanger (distributed model)

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 11

 1.1 Liquid Surge Tank – constant holdup  [State equations]
Fi

F Assumptions
‐ constant density
h F  volumetric flow rate
A r  density

Overall mass balance
dM d ( rV ) d ( rAh ) dh F =F dh
= = = ri Fi - rF r cte
¾¾ ¾ A = Fi - F ¾¾i ¾¾
 A =0
dt dt dt dt dt

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 12

 1.2 Liquid Surge Tank – variable holdup  [State equations]
Fi

1 F  volumetric flow rate Assumptions

r  density ‐ constant density
h
A Lp , Ap F
kv 2

Overall mass balance
d ( rV ) d ( rAh ) dh
dt
=
dt
= ri Fi - rF r cte
¾¾ ¾ A
dt
= Fi - F F?
Bernoulli equation 
2
P1 v12 P2 v22 Lv é Darcy Eq ù
+ + h1 = + + h2 + h f ,1-2 h f ,1-2 = hpipe + hvalve hpipe = f ë û
rg 2g rg 2g D 2g
v2 Leq v 2
hvalve = kv = f
2g D 2g

P2 - P1 v22 - v12 L v22 Leq v22 v22 é L + Leq ù F =A v

h1 - h2 = h = + +f +f ¾¾ h = ê1 + f ú ¾¾ ¾p ¾
2

rg 2g D 2g D 2g 2g ê D ú
êë úû
v2 >> v1
0
8 é L + Leq ù
2ê ú
h = 2 4 F2 ê 1 + f ú
g p Dp ëê D ûú
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 13
 1.2 Liquid Surge Tank – variable holdup  [State equations]
Fi

1 F  volumetric flow rate Assumptions

r  density ‐ constant density
h
A Lp , Ap F
kv 2
8 é L + Leq ù
2ê ú
Bernoulli equation  h = F ê 1 + f ú
g p2Dp4 êë D úû

1 ék D 2.51 ù é Colebrook Eq ù
Turbulent Flow: = -2 log êê + ú
ú ë û
f 3.7 Re f
ëê ûú

1
h  Kt F 2 ¾¾ F = h ¾¾ F = Rt h
Kt
64
Laminar Flow: f =
Re
é L + Leq ù é L + Leq ù é L + Leq ù
8
h = 2 2 F êê 1 + f 2 ú  8 F2 ê f ú = 8 F 2 ê 64mpD ú
g p Dp D ú g p2Dp2 ê D ú g p2Dp2 ê 4rF D ú
ëê ûú ëê ûú ëê 2 ûú

128m ( L + Leq ) 1
h  F = Kl F2 ¾¾ F = h ¾¾ F = Rl h
g pDp4 Kl

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 14

 1.3 Liquid Surge Tank – with pump [State equations]
Fi

1 F  volumetric flow rate Assumptions

r  density ‐ constant density
h
F
A Lp , Ap
kv 2
H p = M - NF 2
Overall mass balance
d ( rV ) d ( rAh ) dh
dt
=
dt
= ri Fi - rF r cte
¾¾ ¾ A
dt
= Fi - F F?
Bernoulli equation 
2
P1 v12 P2 v22 Lv é Darcy Eq ù
+ + h1 + H p = + + h2 + h f ,1-2 h f ,1-2 = hpipe + hvalve hpipe = f ë û
rg 2g rg 2g D 2g
v2
hvalve = kv
Leq v22 2g
P2 - P1 v22 - v12 L v22
( h1 - h2 ) + ( M - NF ) = 2
+ +f +f ¾¾
rg 2g D 2g D 2g
v2 >> v1
0
é L + Leq ù 8 é L + Leq ù
v22 h + ( M - NF 2 ) = 2ê ú
h + ( M - NF ) =
F =Apv2 F 1 + f
2 ê1 + f ú ¾¾ ¾ ¾ ê ú
2g ê D ú g p 2Dp4 êë D úû
ëê ûú

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 15

 1.3 Liquid Surge Tank – with pump [State equations]
Fi

1 F  volumetric flow rate Assumptions

r  density ‐ constant density
h
F
A Lp , Ap
kv 2
H p = M - NF 2
Bernoulli equation 
8 é L + Leq ù
h + ( M - NF 2
)= F2
2 ê1 + f
ê
ú
ú
 Kt F 2 ¾¾ h + ( M - NF 2 )  Kt F 2 ¾¾
g p2Dp4 ëê D ûú

h +M M
F 2 éë Kt + N ùû  h + M ¾¾ F  M >>h
¾¾ ¾ ¾ F 
Kt + N Kt + N

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 16

 2.1 Stirred tank heater – constant holdup [State equations]                            
Fi ,Ti
F  volumetric flow rate Assumptions
F ,T r  density ‐ perfect mixing
‐ perfectly insulated
Total mass : rV = rAh ‐ Kinetic and potential energy neglected
h
‐ pV ~ cte
Total energy : rVcp (T - Tref )
Qstm

Overall mass balance
d ( rV ) d ( rAh ) dh F =F dh
= = ri Fi - rF r cte
¾¾ ¾ A = Fi - F ¾¾i ¾¾
 A =0
dt dt dt dt

Overall energy balance

d (U ) d (H ) d éë rAhcp (T - Tref ) ùû
i p (Ti - Tref ) - rFc p (T - Tref ) + Qstm ¾¾ ¾ ¾
r,cp cte
 = = ri Fc 
dt dt dt

d é
rcpA i p (Ti - Tref ) - rFc p (T - Tref ) + Qstm
h (T - Tref ) ùû = ri Fc rearranging
ë ¾¾ ¾ ¾ ¾
dt

d é Qstm
A h (T - Tref ) û
ù = Fi (Ti - Tref ) - F (T - Tref ) +
dt ë rcp

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 17

 2.1 Stirred tank heater – constant holdup [State equations]                            
Fi ,Ti
F  volumetric flow rate Assumptions
F ,T r  density ‐ perfect mixing
‐ perfectly insulated
Total mass : rV = rAh ‐ Kinetic and potential energy neglected
h
‐ pV ~ cte
Total energy : rVcp (T - Tref )
Qstm

Overall energy balance
A
d é
h (T - T ) ù = F (T - T ) - F (T - T ) + Qstm product rule
¾¾ ¾ ¾ ¾
dt ë ref û i i ref ref
rcp

dh
d dh d Q A =0
A éë h (T - Tref ) ùû = (T - Tref ) A + Ah éëT - Tref ùû = Fi (Ti - Tref ) - F (T - Tref ) + stm ¾¾dt¾ ¾
dt dt dt rcp

dT Q dT Q
Ah = F (Ti - Tref ) - F (T - Tref ) + stm
simplifying
¾¾ ¾¾¾  Ah = F (Ti - T ) + stm
dt rcp dt rcp

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 18

 2.2 Stirred tank heater – variable holdup [State equations]                            
Fi ,Ti F  volumetric flow rate
Assumptions
r  density ‐ perfect mixing
Total mass : rV = rAh ‐ perfectly insulated
‐ Kinetic and potential energy neglected
h Total energy : rVcp (T - Tref ) ‐ pV ~ cte
F ,T
Qstm

Overall mass balance
d ( rV ) d ( rAh ) dh
= = ri Fi - rF r cte
¾¾ ¾ A = Fi - F
dt dt dt

Overall energy balance

d (U ) d (H ) d éë rAhcp (T - Tref ) ùû
i p (Ti - Tref ) - rFc p (T - Tref ) + Qstm ¾¾ ¾ ¾
r,cp cte
 = = ri Fc 
dt dt dt

d é
rcpA i p (Ti - Tref ) - rFc p (T - Tref ) + Qstm
h (T - Tref ) ùû = ri Fc rearranging
ë ¾¾ ¾ ¾ ¾
dt

d é Qstm
A h (T - Tref ) û
ù = Fi (Ti - Tref ) - F (T - Tref ) +
dt ë rcp

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 19

 2.2 Stirred tank heater – variable holdup [State equations]                            
Fi ,Ti F  volumetric flow rate
Assumptions
r  density ‐ perfect mixing
Total mass : rV = rAh ‐ perfectly insulated
‐ Kinetic and potential energy neglected
h Total energy : rVcp (T - Tref ) ‐ pV ~ cte
F ,T
Qstm

Overall energy balance
d Qstm product rule
A éë h (T - Tref ) ùû = Fi (Ti - Tref ) - F (T - Tref ) + ¾¾ ¾ ¾ ¾
dt rcp

dh
d dh d Q A =Fi -F
A éë h (T - Tref ) ùû = (T - Tref ) A + Ah éëT - Tref ùû = Fi (Ti - Tref ) - F (T - Tref ) + stm ¾¾dt¾ ¾ ¾
dt dt dt rcp

dT Qstm
(T - Tref )( Fi - F ) + Ah dt = Fi (Ti - Tref ) - F (T - Tref ) + rearranging
¾¾ ¾ ¾ ¾
rcp

dT Qstm
= Fi (Ti - Tref ) - F (T - Tref ) - (T - Tref )( Fi - F ) + simplifying
Ah ¾¾ ¾¾¾ 
dt rcp

dT Qstm dT Q
Ah = FT
i i - FT
i + ¾¾ Ah = F (Ti - T ) + stm
dt rcp dt rcp

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 20

 2.2 Stirred tank heater – variable holdup [State equations]                            
Fi ,Ti F  volumetric flow rate
Assumptions
r  density ‐ perfect mixing
Total mass : rV = rAh ‐ perfectly insulated
‐ Kinetic and potential energy neglected
h Total energy : rVcp (T - Tref ) ‐ pV ~ cte
F ,T
Q

Summary
dh
Overall mass balance A = Fi - F
dt

dT Q
Overall energy balance Ah = Fi (Ti - T ) +
dt rcp

State variables: h, T
Output variables: h, T
Input variables
Disturbances: Ti , Fi
Manipulated variables: Qstm , F (for feedback control)
Qstm , Fi (for feedforward control)
Parameters: A, r, cp

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 21

 2.1 Stirred tank heater [Temperature Control]                            
F ,Ti
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
TC dh
T Overall mass balance =0
F ,T dt
dT Q
Qstm Overall energy balance Ah = Fi (Ti - T ) + stm
dt rcp

Consider the problem of controlling the temperature T of the liquid. Assume that the 
inlet temperature Ti decreases by 10% form its steady‐state value at time t = 0 and we 
want to keep constant the liquid temperature at Ts manipulating the value of heat 
input Qstm.
dT Q
V = F (Ti - T ) + stm transient energy balance
dt rcp
Q
0 = F (Ti,s - Ts ) + stm,s steady state energy balance
rcp
dT 1
V = F éë (Ti - T ) - (Ti,s - Ts ) ùû + (Qstm - Qstm,s )
dt rcp

dT F 1
= éë (Ti - Ti,s ) - (T - Ts ) ùû + (Qstm - Qstm,s )
dt V rcpV

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 22

 2.1 Stirred tank heater [Temperature Control]                            
F ,T in
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
T
TC Ti,s
T
F ,T

Qstm
t =0 t
Temperature control 

dT F 1
= éë (Ti - Ti,s ) - (T - Ts ) ùû + (Qstm - Qstm,s )
dt V rcpV

The temperature difference (Ts - T ) denotes the error or deviation of liquid’s

temperature from the desired value Ts

To keep the error at 0 value, the heat input Q must be manipulated properly

The simplest control law that can be used to this purpose is:
Proportional Control Law ¾¾Qstm = K p (Ts - T ( t ) ) + Qstm,s

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 23

 2.1 Stirred tank heater [Temperature Control]                            
F ,T in
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
T
TC Ti,s
T
F ,T

Qstm
t =0 t
Temperature control 
dT F 1
P‐control = éë (Ti - T ) - (Ti,s - Ts ) ùû + K p (Ts - T )
dt V rcpV
0
1.4

1.35
-1

1.3

-2
1.25

1.2
-3

1.15

-4 Kp0 = 0
0 0.5 1 1.5 2 1.1
0 0.5 1 1.5 2
Time
Time
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 24
 2.1 Stirred tank heater [Temperature Control]                            
F ,T in
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
T
TC Ti,s
T
F ,T

Qstm
t =0 t
Temperature control 
dT F 1
P‐control = éë (Ti - T ) - (Ti,s - Ts ) ùû + K p (Ts - T )
dt V rcpV
0
1.4
K p1 > K p 0
1.35
-1

1.3

-2
1.25

K p1
1.2
-3

1.15

-4 Kp0 = 0
0 0.5 1 1.5 2 1.1
0 0.5 1 1.5 2
Time
Time
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 25
 2.1 Stirred tank heater [Temperature Control]                            
F ,T in
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
T
TC Ti,s
T
F ,T

Qstm
t =0 t
Temperature control 
dT F 1
P‐control = éë (Ti - T ) - (Ti,s - Ts ) ùû + K p (Ts - T )
dt V rcpV
0
1.4
K p 2 > K p1 > K p 0
1.35
-1
K p2 1.3

-2
1.25

K p1
1.2
-3

1.15

-4 Kp0 = 0
0 0.5 1 1.5 2 1.1
0 0.5 1 1.5 2
Time
Time
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 26
 2.1 Stirred tank heater [Temperature Control]                            
F ,T in
Assumptions
‐ Initially the tank heater is at steady state
‐ Inlet and outlet flowrates are equal
T
TC Ti,s
T
F ,T

Qstm
t =0 t
Temperature control 
dT F 1
P‐control = éë (Ti - T ) - (Ti,s - Ts ) ùû + K p (Ts - T )
dt V rcpV
0
1.4
K p 3 > K p 2 > K p1 > K p 0
1.35
-1 Kp3
K p2 1.3

-2
1.25

K p1
1.2
-3

1.15

-4 Kp0 = 0
0 0.5 1 1.5 2 1.1
0 0.5 1 1.5 2
Time
stirred_tank_heater_T_control.mlx Time
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 27
 EXAMPLE – Gas Surge Drum (I) [State equations] 
q  inlet molar flow rate
n  moles of gas
qi q MW  molecular weight
P
Assumptions
‐ constant molecular weight
‐ ideal gas behavior 
Total mass balance

dM dnMW dn d æç PV ö÷ V dP
= = qi MWi - qMW ¾¾ = qi - q PV =nRT
¾¾ ¾ ¾ ¾
 çç ÷÷ = = qi - q
dt dt dt dt è RT ø RT dt

dP RT
= ( qi - q )
dt V

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 28

 3.1 Continuous Stirred Tank Reactor – Isothermal CSTR  [State equations] 
cAi , Fi

Assumptions
‐ perfectly mixed
h ‐ constant density
cA, F ‐ kinetic and potential energy neglected
‐ pV ~ cte
A ¾¾ B

d ( rV ) r cte dV dV
Overall mass balance = ri Fi - rF ¾¾ ¾¾  r = rFi - rF ¾¾ = Fi - F
dt dt dt

dnA d ( cAV ) product rule

Component A mass balance = = cAi Fi - cAF + rAV ¾¾ ¾ ¾ ¾
dt dt

dV dC A dcA
= cAi Fi - cAF - cA ( Fi - F ) + rAV
in
cA +V = cAi Fi - cAF + rAV dV /dt =F -F
¾¾ ¾ ¾ ¾ ¾ V
dt dt dt

dcA dcA F
V = Fi ( cAi - cA ) + rAV ¾¾ = i ( cAi - cA ) + rA r = a r =-kc
¾¾
A
¾A¾ ¾A¾
dt dt V

dcA F
= i ( cAi - cA ) - kcA
dt V

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 29

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAi , Fi ,Ti [State equations] 
Fc ,Tc
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tci cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

d ( rV ) r cte dV dV
Overall mass balance = ri Fi - rF ¾¾ ¾¾  r = rFi - rF ¾¾ = Fi - F
dt dt dt

d ( cAV ) product rule

Component A mass balance = = cAi Fi - cAF + rAV ¾¾ ¾ ¾ ¾
dt

dV dC A dcA
= cAi Fi - cAF - cA ( Fi - F ) + rAV
in
cA +V = cAi Fi - cAF + rAV dV /dt = F -F
¾¾ ¾ ¾ ¾ ¾ V
dt dt dt

dc dcA Fi rA = aAr =-k (T )cA ; k (T )=k0e -E / RT

V A = Fi ( cAi - cA ) + rAV ¾¾ = ( cAi - cA ) + rA ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ 
dt dt V

dcA F
= i ( cAi - cA ) - k 0e -E /RT cA
dt V

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 30

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAin , F in ,T in [State equations] 
Fc ,Tcout
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tcin cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

dE dU dH
Overall energy balance =  = ri Fihi (Ti ) - rFh (T ) - Q
dt dt dt

The enthalpy of al liquid system is a function of its temperature and composition:
dH æ ¶H ö÷ dT æç ¶H ö÷ dnA æç ¶H ö÷ dnB
H = f (T , nA, nB ) ¾¾
differentiating
¾¾¾¾  = çç ÷ +ç ÷ +ç ÷
dt çè ¶T ø÷
P ,nA,nB dt èç ¶nA ÷ø÷P ,n dt èç ¶nB ÷÷øP ,n dt
A ,nB A ,nB

we also know that…
æ ¶H ö÷ ¶H  T ¶H  T
çç ÷÷ = mcp = rVcp =H A( ) =H B( )
çè ¶T ø ¶n A ¶n B
P ,nA ,nB
Partial molar 
and
dnA d ( cAV ) dnB d ( cBV ) enthalpies
= = cAi Fi - cAF + rAV = = -cB F + rBV
dt dt dt dt

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 31

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAin , F in ,T in [State equations] 
Fc ,Tcout
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tcin cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

Overall energy balance
¶H ¶T ¶H ¶n A ¶H ¶ n B
Substituting the former relations into    dH = + + give rise to
dt ¶T ¶t ¶n A ¶ t ¶n B ¶t

dH dT  T éc F - c F + r V ù + H
 T é -c F + r V ù
= rVcp +H A ( ) ë Ai i A A û B ( )ë B B û
dt dt

and matching the above equation and the total energy balance we get
ri Fihi (Ti ) - rFh (T ) - Q dT
rVcp = rin F inh in (T in ) - rFh (T ) - Q
dT  T éc F - c F + r V ù dt
= rVcp +H A ( ) ë Ai i ¾¾  T é c in F in - c F + r V ù
A( )ê A
A A û -H
dt ë A A úû
 T é -c F + r V ù
+H B ( )ë B B û

- H B (T ) ëé -cB F + rBV ûù

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 32

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAin , F in ,T in [State equations] 
Fc ,Tcout
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tcin cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

Overall energy balance
Rate of energy input into the reactor
 T + r c T -T ù
ri Fihi (Ti ) = Fi éë rihi (T ) + ricpi (Ti - T ) ùû = Fi éê cAi H A( ) i pi ( i ) úû
ë

Rate of energy output from the reactor
 T -c H
rFh (T ) = F éê cA H  T ù
A( ) B ( )ú
ë B û

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 33

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAin , F in ,T in [State equations] 
Fc ,Tcout
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tcin cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

Overall energy balance
dT   
Thus, rVcp i Ai H A (T ) + Fi ric pi (Ti - T ) - FcA H A (T ) - FcB H B (T ) - Q
= Fc
dt
 T Fc + H  T c F -H  T rV
-H A ( ) i Ai A( ) A A( ) A rA = aAr  rA =-kcA
rB = aBr  rB =kcA
  ¾¾ ¾ ¾ ¾ ¾ ¾
B ( )
+H T c F -H T r V
B B ( )B

dT  T -H  T ù rV - Q  -H = é -DH ù
= Fi ricpi (Ti - T ) + éê H
r cte; cp cte; H
rVcp A( ) B ( )ú
A B ë rû
ë û ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾

dt

dT Fi é -DH r ù
= (Ti - T ) + ë ûr - Q
dt V rcp rcpV

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 34

 3.2 Continuous Stirred Tank Reactor – Nonisothermal CSTR 
cAin , F in ,T in [State equations] 
Fc ,Tcout
Assumptions
‐ perfectly mixed
‐ constant density and heat capacity
Fc ,Tcin cA, F ,T ‐ kinetic and potential energy neglected
‐ pV ~ cte

A ¾¾ B DH rec < 0

dV
Summary Overall mass balance = Fi - F
dt
dcA F
Component A mass balance = i (cA - cA ) - k0e -E / RT cA
dt V i

dT F é -DH r ù
= i (Ti - T ) + ë û k e -E /RT c - Q
Overall energy balance dt V rcp 0 A
rcpV

State variables: V , cA, T

Output variables: V , cA, T
Input variables
Disturbances: cAi,Ti , Fi
Manipulated variables: Q, F (for feedback control)
Parameters: r, cp , éë -DH r ùû , k0, E , R

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 35

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Assumptions
‐ perfectly mixed
A, B ‐ constant density and heat capacity
h ‐ pV ~ cte
cA , F3,T3
3

Q
d ( rV ) dV
Overall mass balance = r1F1 + r2F2 - r3F3 r cte
¾¾ ¾¾  = F1 + F2 - F3
dt dt

dnA d ( cAV ) product rule

Component A mass balance = = cA F1 + cA F2 - cA F3 ¾¾ ¾ ¾ ¾
dt dt 1 2 3

dcA dV dV /dt = F + F -F
V + cA = cA F1 + cA F2 - cA F3 ¾¾ ¾ ¾1¾ 2¾ ¾
3

dt dt 1 2 3

dcA
V = cA F1 + cA F2 - cA F3 - cAF1 - cAF2 + cAF3
dt 1 2 3

dcA
V
dt
(1 3
) 1 3
(
= cA - cA F1 + cA - cA F2 )
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 36
 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh (T ) ‐ pV ~ cte
cA , F3,T3
3

Q
dH
Overall energy balance = r ( F1h1 + F2h2 ) - rF3h3 (T ) + Q
dt
d é
ë rVh3 ùû = r ( F1h1 + F2h2 ) - rF3h3 (T ) + Q
dt

How to characterize hi in terms of the state variables T and C ?

We know that
h1 (T1 ) = h1 (Tref ) + cp1 (T1 - Tref ) where Tref is the reference temperature in which
h2 (T2 ) = h2 (Tref ) + cp 2 (T2 - Tref )
 +c H
rh1 (Tref ) = cA H  + c DH
 T
h3 (T3 ) = h3 (Tref ) + cp 3 (T3 - Tref ) A B B A s 1 ( ref )
1 1 1
 +c H
rh2 (Tref ) = cA H  + c DH
 T
s 2 ( ref )
A B
Heats of 
2 B A 2 2 solution per 
 +c H
rh3 (Tref ) = cA H  + c DH
 T
A B B A s 3 ( ref ) mol of A at Tref
3 3 3

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 37

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh (T ) ‐ pV ~ cte
cA , F3,T3
3

Overall energy balance

Combining these two set of equations give rise to
 +c H + c DH
 + rc T - T
rh1 (T1 ) = cA H
1
A B B
1 A s1 p1 ( 1
1 ref )
 +c H + c DH
 + rc T - T
rh2 (T2 ) = cA H
2
A B B
2 A s2 p2 ( 2
2 ref )
 +c H + c DH
 + rc T - T
rh3 (T3 ) = cA H
3
A B B
3 A s3 p3 ( 3
3 ref )

And substituting these relations into the overall energy balance we take
d é æ  +c H  + c DH  ÷ö + V rc T - T ù æ  +c H  + c DH  ö÷ + F rc T - T
êV ççcA H
dt êë è 3
A A3 B A3 s 3 ÷÷
ø p3 ( 3 ref ) ú = F ç
è
c
1 ç A1 H A A1 B A1 s1 ÷
ø÷ 1 p1 ( 1 ref )
ûú
æ  +c H  + c DH  ö÷ + F rc T - T æ  +c H  + c DH  3 ö÷ - F rc T - T
2 p2 ( 2 ref ) 3 p3 ( 3 ref ) + Q
+ F2 ççcA H A A2 B s2 ÷ - F ç
3ç c H s ÷
è 2 A2 ÷ø çè A3 A A3 B A3 ÷ø

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 38

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh (T ) ‐ pV ~ cte
cA , F3,T3
3

Q
d é  d éêVc ùú + H  d éêVc ùú + H  d é ù
Overall energy balance rcp 3
dt ë
V (T 3 - Tref ) ù +H
û A
dt êë A3ú
B
dt êë B 3ú
s3
dt
êVcA ú =
êë 3ú
û û û
 + Fc H  + F c DH  + F rc T - T
= F1cA H
1
A 1 B B
1 1 A 1
s1 1 p1 ( 1 ref )

 +Fc H  + F c DH
 + F rc T - T
+ F2cA H A
22 B B 2 A 3
s2 2 p2 ( 2
2 ref )
 -Fc H  - F c DH
 - F rc T - T
- F3cA H A
33 B B 3 A 3
s3 3 3( 3 3 ref ) + Q

d é d é
ë cAV ùû ë cBV ùû
dt dt

d é  êé d éVc ù - d ù  éd é
éVc ù ú + H ù d é ù
ù  d é
+ H s 3 êVcA ùú =
rcp 3
dt ë
V ( 3 ref ) û
T - T ù + H A
êë dt êë A 3 úû dt ëê A ûú úû B ê ê
êë dt ë
VcB 3 ú -
û dt ê
ë
VcB ú
û
ú
úû dt ë 3û

 + F rc T - T  
= F c DH
1 A1 s1 1 p1 ( +Fc
1 ref ) 2 A DH s 2 + F2rc p 2 (T2 - Tref ) - F3cA DH s 3 - F3rc p 3 (T3 - Tref ) + Q
2 3

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 39

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh (T ) ‐ pV ~ cte
cA , F3,T3
3

Q
dV d é
rcp 3 (T3 - Tref ) dt + rcp 3V ëT3 - Tref ùû =
Overall energy balance dt
 + F rc T - T
= F1cA DH
1
s1 1 p1 ( 1 ref )
 + F rc T - T
2 p2 ( 2 )
product rule
¾¾ ¾¾¾¾¾¾¾¾¾  + F2cA DH s2 ref
d éVC ù /dt =c F +c F -c F
ë Aû A1 1 A2 2 A3 3
2
 - F rc T - T
- F3cA DH
3
s3 3 p3 ( 3 ref ) + Q

 - F c DH
- F1cA DH  + F c DH

s3 2 A s3 3 A s3
1 2 3

rearranging…
rcp3 (T 3
-T ref
) dV + rcp3V
d é 3 ref ù = F 1c1 éê DH  3 ùú + F 2c 2 éê DH
 1 - DH  3 ùú
 2 - DH
dt dt êëT - T úû A
êë
s s
úû A
êë
s s
úû
+ F 1rc1p (T 1 - T ref ) + F 2rcp2 (T 2 - T ref ) - F 3rcp3 (T 3 - T ref ) + Q

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 40

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh 3 (T ) ‐ pV ~ cte
cA , F3,T3
3

Q
dT3  - DH
 ù +Fc  - DH
 ù
Overall energy balance rcp 3V = F1cA éê DH s1 s3 ú
é DH
êë s2 s3 ú
dt 1 ë û 2 A2 û
+ F1rcp1 (T1 - Tref ) + F2rcp 2 (T2 - Tref ) - F3rcp 3 (T3 - Tref )
dV /dt =F1 +F2 -F3
¾¾d é¾ ¾ ¾ ¾ ¾
êëT3 -Tref ùúû =dT3 - F1rcp1 (T3 - Tref ) - F2rcp 2 (T3 - Tref ) + F3rcp 3 (T3 - Tref ) + Q

dT3  - DH  ù + F 2c é DH  - DH  ù
rearranging… rcp 3V = F1cA éê DH s1 s3 ú ê s2 s3 ú
dt 1 ë û A 2 ë û
+ F1r éë cp1 (T1 - Tref ) - rcp 3 (T3 - Tref ) ùû + F2r éë cp 2 (T2 - Tref ) - cp 3 (T3 - Tref ) ùû + Q

Lastly, if we assume that  cp1 = cp2 = cp 3 = cp

dT3  - DH
 ù +Fc  - DH ù + F rc T - T + F rc T - T + Q
rcpV = F1cA éê DH s1 s3 ú
é DH
êë s 2 s3 ú 1 p( 1 3) 2 p( 2 3)
dt 1 ë û 2 A2 û

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 41

 4.1 Mixing Process – variable holdup [State equations] 
cA , F1,T1 cA , F2,T2
1 2

Total enthalpy of the Assumptions

‐ perfectly mixed
material in the tank
A, B ‐ constant density and heat capacity
h H = rVh (T ) ‐ pV ~ cte
cA , F3,T3
3

Summary
dV
Overall mass balance = F1 + F2 - F3
dt
dcA F æ ö F æ ö
Component A mass balance = 1 ççcA - cA ÷÷÷ + 2 ççcA - cA ÷÷÷
dt Vè 1 3ø V è 2 3ø

F1cA F2cA
dT3 1  - DH
é DH  ù+ 1  - DH
é DH  ù
Overall energy balance = êë s 1 s 3 úû rc V êë s2 s3 ú
dt rcpV p
û

F1 F Q
+ (T1 - T3 ) + 2 (T2 - T3 ) +
V V rcpV
 dT F1 F
If the heats of solutions are independent of the concentrations,  Q
3
= (T1 - T3 ) + 2 (T2 - T3 ) +
then the energy balance is as follows  dt V V rcpV
Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 42
 5 Tubular Heat Exchanger [State equations]  [distributed parameter system]
v  average velocity of the liquid
steam D  external diameter of the inner tube
z in
Tstm A  cross - sectional area
Q  heat transferred per unit of time and unit of heat transfer area

liquid Assumptions
T T z +Dz ‐ Temperature does not change along the 
z
Tcin Tcout
Dz radius of the pipe

The temperature of the liquid changes with time and also along the axial direction z. 
Thus, we have two independent variables: z and t  T ( z , t )

Overall energy balance
Amount of enthalpy accumulated over the time interval  éë t + Dt ùû  rcpADz éêT - T t ùú
ë t +Dt û
z
Amount of enthalpy in at    with flowing fluid over the time 
 rcpvA (T - T ref ) z Dt
interval  éë t + Dt ùû
é z + Dz ù
Amount of enthalpy out at                 with flowing fluid over the 
ë û  rcpvA (T - T ref ) z +Dz Dt
é ù
time interval  ë t + Dt û
Enthalpy in through the heat exchanger wall over time interval éë t + Dt ùû  Q ( pDDz ) Dt

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 43

 5 Tubular Heat Exchanger [State equations]  [distributed parameter system]
v  average velocity of the liquid
steam D  external diameter of the inner tube
z in
Tstm A  cross - sectional area
Q  heat transferred per unit of time and unit of heat transfer area

liquid Assumptions
T T z +Dz ‐ Temperature does not change along the 
z
Tcin Tcout
Dz radius of the pipe

Overall energy balance rcpADz êéT - T t ùú = rcpvA (T - T ref ) z Dt - rcpvA(T - T ref ) z +Dz Dt

ë t +Dt û
+ Q ( pD Dz ) Dt
dividing through  Dt Dz
éT
ê - T ù
ú (T - T ref )z (T - T ref ) z +Dz
rcpA ë t +Dt tû
= rcpvA - rcpvA + Q ( pD )
Dt Dz Dz

æ ¶T ö÷ æ ¶T ÷ö æ ¶T ö÷ æ ¶T ÷ö Q ( pD )
mean value theorem of  rcpA çç ÷÷ = -rcpvA çç ÷ + Q ( pD ) ¾¾ çç ÷÷ + v çç ÷÷ +
çè ¶t ø çè ¶z ÷ø çè ¶t ø èç ¶z øt rcpA
differential calculus z t z

f ( x ) x +Dx - f ( x )x æ ö æ ö
= f ' (x )
Q =U (T
¾¾ ¾ ¾
stm
¾ ¾
-T )
çç ¶T ÷÷ + v çç ¶T ÷÷ = U pD (T - T )
Dx çè ¶t ø÷ èç ¶z ÷øt rcpA stm
z

Chemical process control [34528] Chapter 2: Development of Mathematical Models Academic year 2021/22 44