MATHEMATICAL FORMULATION OF PHYSICOCHEMICAL

PROBLEMS

Objective: Students have capability to develop mathematical

formulation of Physicochemical problems and solve the
mathematical problems using known mathematical methods.
 MATHEMATICAL FORMULATION
The mathematical treatment of engineering problems involves three basic
steps: the expression of the problem in mathematical language, the solution of
mathematical problems, and the interpretation of the results.

Physicochemical Problems

Assumption
Law Conservation
Rate
Mathematical Formulation
Equilibrium

Solution of Mathematical Formulation Analytical

Numerical

Interpretation
FUNDAMENTAL LAWS
There are three basic physical and chemical law, they are: Conservation law,
Rate expression, and Equilibrium relation.

CONSERVATION LAWS
Mass, Overall:

Rate of mass accumulation in system = Rate of mass in – Rate of mass out

Mass, Component:

Rate of mass accumulation of component i in system = Rate of mass of

Component i in – Rate of mass of component i out +Rate of mass generation
of Component i
Energy
Rate of Energy Accumulation = Rate of Energy in – Rate of Energy out +
Rate of Energy Generation
Momentum
Rate of Momentum Accumulation = Rate of Momentum in – Rate of Momentum
Out + Rate of Momentum Generation

Body Force Surface Force

FUNDAMENTAL LAWS
RATE EXPRESSION

Heat Transfer
T
Conduction q x = −kA
x
Convection (Interface Transport) q = hA(Ts − Tf )
Mass Transfer
C A
Diffusion : N Ax = −D A S
x
Convection (Interface Transport): N A = k CS(C AS − C Ab )
Momentum Transfer
U y
Molecular (Newtonian) :  xy = −
x

Interface Transport  = K.f

Chemical Reaction
aA + bB → cC − rA = kC A CB
FUNDAMENTAL LAWS
EQUILIBRIUM RELATION

Phase Equilibrium : Vapor-liquid ------- Raoult Law

Liquid-liquid
Gas/vapor-solid
Liquid-solid

Chemical Equilibrium

aA + bB  cC
C cC
K= a b
CACB
LUMP PARAMETER AND DISTRIBUTED PARAMETER MODELS
Mathematical models can be classified into two distinct types: Lump parameter and
Distributed parameter models. The first type is characterized by the uniformity of
the parameter value in the system such as mixed flow reactor, while the second
type is characterized by the variability of the variable/parameter value in the system
such as plug flow reactor. The distributed parameter model is usually called
Transport Phenomena models, because it involves the phenomena of heat, mass
or momentum transport. For the distributed parameter models, we have to consider
more specifically on the boundary condition of the system.

CSTR PFR
C1, T1, Cp1, dst
Control volume
CX1, TX1 CX2, TX2 CX3, TX3

C1, T1, Cp1, dst

 GENERAL TYPE OF BOUNDRY CONDITION

HEAT TRANSFER

1. The temperature at a surface may be specified

2. The heat flux at a surface may be given, e.g. q=qo. When a surface is assumed
completely isolated, then the heat flux at that surface is equal to zero.
3. At solid-fluid interface the heat flux may related to the difference between the
temperature at the interface and that in the fluid, thus

q = h(T − Tfluid ) h=heat transfer coefficient

4. At solid-solid interface, the continuity of temperature and the normal

component of the heat flux may be specified.
5. At plane, axes or point of symmetry, the heat flux is equal to zero, except
the symmetry is treated as the heat source.
 GENERAL TYPE OF BOUNDRY CONDITION

MASS TRANSPORT

1. The concentration at a surface can be specified.

2. The mass flux at a surface can be specified.
3. If diffusion is occurring in a solid, it may happen that at the solid surface
substance A is lost to a surrounding fluid stream according to the relation,

N A0 = k c (C A0 − C Af ) kc = mass transfer coefficient

4. The rate of chemical reaction at the surface can be specified. For example,
if a substance A disappears at a surface by a first-order chemical reaction,
N A0 = k1"C A

5. At the plane, axes, or point of symmetry the mass flux is equal to zero.
GENERAL TYPE OF BOUNDRY CONDITION

MOMENTUM TRANSPORT

1. At solid-fluid interfaces the fluid velocity equals the velocity with which the
surface itself is moving.
2. At liquid-gas interface, the momentum flux (hence the velocity gradient)
is equal to zero.
3. At liquid-liquid interfaces the momentum flux perpendicular to the interface,
and the velocity, are continuous across the interface.
4. At the plane, axes, or point of symmetry the momentum flux is equal to zero.

Gas-liquid interface

liquid Solid-Liquid interface

GENERAL STEPS
1. Draw the sketch of the system to be modeled and label/define the various
geometric, physical and chemical quantities.
2. Carefully select the important variables, and list the parameters that are expected
to be important
3. Establish a ”control volume” for a differential or finite element of the system to
be modeled.
4. Write the conservation law on the control volume and use the necessary rate
expression and equilibrium relation to derive equations describing the system.
5. Write boundary and initial condition
6. Solve the equations
7. Interpret the solution
 ILLUSTRATIVE EXAMPLES (1)
Two tanks each contains 100 liters salt solution (20 gr/lit). A stream of water is fed
into the first tank at a rate of 5 liters/min. The liquid flows from the tank to the
second tank at a rate of 8 liters/min. The liquid flows from the second tank at a rate
of 8 liters/min where part of it (3 liters/min) is directed to the first tank and the
balance flows to some points out of the system. Determine the salt concentration
(gr/lit) in the first and second tank as a function of time. Assume  is constant in all
streams.

SOLUTION

5 lt/min

8 lt/min

5 lt/min
ILLUSTRATIVE EXAMPLES (1)
Tank II
Tank I:
Consevation of mass (overall) Consevation of mass (overall)

d
V = 5 + 3 − 8 = 0
d
V2  = 8 − 8 = 0
dt
dt
dV2
dV1 =0 V2 = const = 100
 =0 V1= const = 100 dt
dt
Conservation of mass (salt) Conservation of mass (salt)
d
V1C1  = 5,0 + 3C 2 − 8C1 = 0 d
V2 C 2  = 8C1 − 8C 2
dt dt
dC1
100 = 3C 2 − 8C1 (1) 100
dC 2
= 8C1 − 8C 2
dt dt
(2)
dC 2
C1 = C 2 + 12.5
dt
 ILLUSTRATIVE EXAMPLES (1)
Initial Condition: t=0 C1=20, C2 = 20

Eq (2) is differentiated with respected to t: Initial Condition:

dC1 dC2 d 2C2 dC 2
= + 12.5 2 (3) t=0 C2=20 =0
dt dt dt dt

Eq. (2) is substituted into Eq. (1): C2 = 20 = K1 + K2 K1 = 26.33

dC2 d 2C2 dC 0 = - 0.031 K1 – 0.129 K2 K2 = - 6.33

100 + 1250 2 = 3C 2 − 8C 2 − 100 2
dt dt dt
2

250
dC
+ 40
dC 2
+C =0 2
2
C2 = 26.3261e −0.31t − 6.33e −0.129t
2
dt dt
m1 = - 0.031 ; m2 = - 0.129 :

C 2 = K1e −0.031t + K 2 e −0.129t (4) C1 = 16.125e−0.031t + 3.875e−0.129t

dC 2
= −0.031K 1e −0.031t − 0.129 K 2 e −0.129 t (5)
dt
Assigments
1. Initially, a tank contain 500 kg of salt solution containing 10 % salt. A stream enters at constant
flow rate of 10 kg/h containing 20 % salt. A stream leaves at a constant rate 5 kg/h. The tank is
well stirred. Derive an equation relating the weight fraction wA of the salt in the tank at any
time t in hours.
2. A well stirred storage vessel contains 10000 kg of solution of a dilute methanol solution (wA =
0.05 mass fraction alcohol). A constant flow of 500 kg/min of pure water is suddenly introduced
into the tank, and a constant rate of withdrawal of 500 kg/min of solution is started. These two
flow are continued & remain constant. Assuming that the densities of the solutions are the
same and that the total contents of the tank remain constant at 10000 kg of solution, calculate
the time for the alcohol to drop to 1.0 wt%.
Assigments
3. A storage vessel is well stirred and contains 500 kg of total solution with concentration 5% salt.
A constant flow rate of 900 kg/h of salt solution containing 16.67 % salt is suddenly introduced
into the tank and a constant withdrawal rate 600 kg/h is also started. These two flows remain
constant thereafter. Derive an equation relating the outlet withdrawal concentration as
function of time. Also, calculate the concentration after 2.0 h.
Assigments
4. A tank initially contains 100 ft3 of fresh water. Then, 2 ft3 of brine of having a concentration of 1
pcf (1 lb/ft3) of salt, is run into the tank per minute, and the mixture, kept uniform by mixing,
runs out at the rate of 1 ft3/min. What will be the exit brine concentration when the tank
contains 150 ft3 of brine.
5. A tank with a capacity of 1000 L, is initially containing 100 L of water. At one point, it was filled
with a salt solution with a concentration of 10 g/L at a flowrate of 20 L/min. What is the volume
of the solution in the tank and how much it coressponding concentration after 30 minutes.
Assigments
6. Three tanks of 25 m3 capacity are each arranged so that when water is fed into the first an
equal quantity of solution overflows from the first to the second tank, likewise from the second
to the third, and from the third to some point out of the system. Agitators keep the contents of
each tank uniform in concentration. To start, let each of the tank be full of a salt solution of
concentration 100 kg/m3. Run water into the first tank at 0.2 m3/min , and let the overflows
functions as described above. Calculate the time required to reduce the salt concentration in
the first tank to kg/m3. Calculate the concentrations in the other two tanks at this time.
ILLUSTRATIVE EXAMPLES (2)

(a) A container is maintained at a constant temperature of 800o F and is fed with a

pure gas A at a steady rate of 1 lbmole/min; the gas product gas stream is
withdrawn from the container at the rate necessary to keep the total pressure
constant at a value of 3 atm. The container contents are vigorously agitated, and
the gas mixture is always well mixed. The following irreversible second order gas
phase reaction occurs in the container:

2A → B
At a temperature of 800 oF, the reaction rate constant for the reaction has the
numerical value of 1000 ft3 /(lbmole min). Both A and B are perfect gases.
Because of their low temperature, no reaction occurs in the lines to and from the
vessel. If under steady state condition, the product stream is to contain 1/3
mole % B, how large (in cubic feet) should be the volume of the reaction container ?

(b) After the steady state of a) has been attained, the valve on the exit pipe of
isothermal vessel is abruptly closed. The feed rate is controlled so that the total tank
pressure is maintained at 3 atm. If the mixing is still perfect, how many minutes will it
take (after the instant of closing the valve) for the tank content to be 90 mole % B. The
feed rate is controlled so that the total tank pressure is maintained at 3 atm.
 ILLUSTRATIVE EXAMPLES (2)
Solution
a)
Mass Balance:
n 2A
P = 3 atm
A: 0 = 1 − FAf − k 2 V
Feed Product V n 2A
T = 800oC 2FBf = k 2 V
A V
A, B 1 n 2A
B: 0 = 1 − FBf − k 2 V
2 V

0 = 1 − FAf − 2FBf
2
n 0 = 1 − FAf − FAf
0 = 1 − 0.5 − k A
2
V
V FBf 1
2 FBf = FAf =
FAf + FBf 3
FAf = 0.5
PA V y A PV
nA = =
RT RT
2 (2 / 3) 2 32V (0.5)(0.7302) 2 (1260) 2
yA = 0 = 1 − 0.5 − (1000) V= 2 2
= 105.8
3 R 2T 2 (1000)(2 / 3) (3)
 ILLUSTRATIVE EXAMPLES (2)
Solution
a)
Mass Balance:
n 2A
P = 3 atm
A: 0 = 1 − FAf − k 2 V
Feed Product V n 2A
T = 800oC 2FBf = k 2 V
A V
A, B 1 n 2A
B: 0 = 1 − FBf − k 2 V
2 V

0 = 1 − FAf − 2FBf
2
n 0 = 1 − FAf − FAf
0 = 1 − 0.5 − k A
2
V
V FBf 1
2 FBf = FAf =
FAf + FBf 3
FAf = 0.5
PA V y A PV
nA = =
RT RT
2 (2 / 3) 2 32V (0.5)(0.7302) 2 (1260) 2
yA = 0 = 1 − 0.5 − (1000) V= 2 2
= 105.8
3 R 2T 2 (1000)(2 / 3) (3)
 ILLUSTRATIVE EXAMPLES (2)
Solution

b) Mass Balance:
A: dn A n 2A
= FAo − k 2 k n A2 dn A n 2A
dn kn
dt V
= FA0 − =0 A FA0 = 2 = −k
dnB k n A2 dt 2V 2V dt V
B: = 0+
dt 2V
t=0
1 k PA V y A PV (2 / 3) * 3 *105.8
dn A k − =− t+K nA = = = = 0.2287  0.23
 n 2 = −  2Vdt nA 2V RT RT (0.7302)(1260)
A

1 K = −4.348
− = 0+K
0.23

1
= 4.726 t + 4.348 1 1000
0.0345 − =− t − 4.348
nA 2 * (105.8)
0.1* 3 *105.8
t=?→ nA = 0.0345 nA = = 0.0345
t=5.213 (0.7302)(1260) 1
= 4.726t + 4.348
nA
 ILLUSTRATIVE EXAMPLES (3)
Disk shaped catalyst is used to accelerate the following irreversible first-order reaction :
A → B

The concentration of A at the catalyst surface is CAS. The effective diffusivity A trough the
catalyst is DA
a) Determine concentration distribution of A in the catalyst
b) Derivate an equation to estimate the mass transfer rate of A into the catalyst

Solution
a)
N AZ CAS Mass Balance:
N AZ Z = Z + Z
Z= Z
0 = N AZ Z= Z
− N AZ Z = Z + Z
− kC A ZS

Z ( N AZ − N AZ )
Z 0=− Z = Z + Z Z= Z
− kC A ZS
ZS

As Z→0

1 dN AZ
CAS 0 = −( − kC A )
S dZ
 ILLUSTRATIVE EXAMPLES (3)

1 d  dC A  d 2 CA k
0=−  − DA S − kC A − CA = 0 k k
S dZ  dZ  Z − Z
dZ 2 DA C A = K1e DA
+ K 2e DA

dC A
B.C.1: Z = 0, =0 C AS
dZ  K1 = K 2 = dC A k
k
Z k −
k
Z
= K1 − K2
k k
B − B e DA
e DA
e DA
+ e DA
dZ DA DA
B.C.2: Z = B, C A = C AS

C AS  k
Z −
k
Z 
CA = e DA
+ e DA

 
k k
B − B
e DA
+ e DA

dC A  k
 k
−
k  
b) N AZ Z =B = − D A S Z =B = − D AS 
C AS DA
e DA
Z
− e DA
Z
 
dZ  B   
k k
−
 e DA
B
+ e DA   Z = B 

k  k 
= − D AS C A S tanh  B 
DA  DA 