Model

Impact of simulation on chemical process industries

Systematic Model Buildings
Classification of mathematical models- steady state Vs dynamic models, lumped Vs distributed
parameter models, deterministic Vs stochastic models.

❑ Steady State vs Dynamic

❑ Linear vs Non-Linear
❑ Lumped vs Distributed
❑ Continuous vs Discrete
❑ Deterministic vs Probabilistic

Steady state and Dynamic

Static Model v/s Dynamic Model

Why dynamic behaviour?

Linear Model v/s Non-Linear Model

Deterministic Process:
1. The observables take on a continuous set of values in a well-defined manner
2. The output variable most representative of the process uniquely determined by input
variable
3. These process can be adequately described by classical analysis and numerical methods
4. Example: CSTR

Probabilistic (Stochastic) Process

1. The observables change in a random manner and often discontinuously
2. The output variable is not directly related to the input variable
3. These processes are described in terms of statistics and probabilistic theory
4. Example: contact catalytic process in which the yield of the product diminishes
with decrease in the activity in catalyst as it ages with time and the pulse properties.
Principles of Formulation
A. BASIS.
The bases for mathematical models are the fundamental physical and chemical laws, such as the
laws of conservation of mass, energy, and momentum. To study dynamics we will use them in
their general form with time derivatives included.
B. ASSUMPTIONS.
Probably the most vital role that the engineer plays in modelling is in exercising his engineering
judgment as to what assumptions can be validly made. Obviously an extremely rigorous model
that includes every phenomenon down to microscopic detail would be so complex that it would
take a long time to develop and might be impractical to solve, even on the latest super computers.
C. MATHEMATICAL CONSISTENCY OF MODEL.
Once all the equations of the mathematical model have been written, it is usually a good idea,
particularly with big, complex systems of equations, to make sure that the number of variables
equals the number of equations. The so-called “degrees of freedom” of the system must be zero in
order to obtain a solution. If this is not true, the system is underspecified or over specified and
something is wrong with the formulation of the problem.
D. SOLUTION OF THE MODEL EQUATIONS.
The available solution techniques and tools must be kept in mind as a mathematical model is
developed. An equation without any way to solve it is not worth much.
E. VERIFICATION.
An important but often neglected part of developing a mathematical model is proving that the
model describes the real-world situation. At the design stage this sometimes cannot be done
because the plant has not yet been built. However, even in this situation there are usually either
similar existing plants or a pilot plant from which some experimental dynamic data can be
obtained. The design of experiments to test the validity of a dynamic model can sometimes be a
real challenge and should be carefully thought out.

FUNDAMENTAL LAWS
Continuity Equations
A. TOTAL CONTINUITY EQUATION (MASS BALANCE).
The principle of the conservation of mass when applied to a dynamic system says
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑇𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑖𝑛𝑠𝑖𝑑𝑒 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 (1)

Units are Mass per time

Example 2.1. Consider the tank of perfectly mixed liquid shown in Fig. 2.1 into which flows a
liquid stream at a volumetric rate of F0 (ft3/min or m3/min) and with a density of ρ0(lbm/ft3 or
kg/m3). The volumetric holdup of liquid in the tank is V (ft3 or m3), and its density is ρ. The
volumetric flow rate from the tank is F, and the density of the outflowing stream is the same as
that of the tank’s contents. Develop a total continuity equation for the liquid phase in the tank.

Solution:
This a macroscopic system, as opposed to a microscopic system, since it is of definite and finite
size. The mass balance is around the whole tank, not just a small, differential element inside the
tank.
𝐹0 𝜌0 − 𝐹𝜌 = 𝑡𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝜌𝑉 (2)
The units of this equation are lbm/min or kg/min.
Liquid is perfectly mixed, the density is the same everywhere in the tank
It does not vary with radial or axial position; i.e., there are no spatial gradients in density in the
tank.
This is why we can use a macroscopic system. It also means that there is only one independent
variable, t.
Since p and V are functions only of t, an ordinary derivative
𝑑(𝜌𝑉)
= 𝐹0 𝜌0 − 𝐹𝜌 (3)
𝑑𝑡

Z=0 Z Z+dz z=L

Fig.2.2. Flow through a pipe.

Example 2.2. Fluid is flowing through a constant-diameter cylindrical pipe sketched in Fig. 2.2.
The flow is turbulent and therefore we can assume plug-flow conditions, i.e., each “slice” of liquid
flows down the pipe as a unit. There are no radial gradients in velocity or any other properties.
However, axial gradients can exist. Density and velocity can change as the fluid flows along the
axial or z direction. There are now two independent variables: time t and position z. Density and
velocity are functions of both t and z. ρ=ρ(t,z) and v=v(t,z). Apply the total continuity equation
[Eq.1] to a system that consists of a small slice.
Solution:
The system is now a “microscopic” one. The differential element is located at an arbitrary spot z
down the pipe. It is dz thick and has an area equal to the cross-sectional area of the pipe A (ft2 or
m2).
𝜕(𝐴𝜌𝑑𝑧)
Time rate of change of mass inside system: 𝜕𝑡
(4)

A dz is the volume of the system; ρ is the density. The units of this equation are lbm/min or
kg/min.
Mass flowing into system through boundary at z: 𝑣𝐴𝜌 (5)
𝜕(𝑉𝐴𝜌)𝑑𝑧
Mass flowing out of the system through boundary at z + dz : 𝑣𝐴𝜌 + (6)
𝜕𝑧

From eq.(1)
𝜕(𝐴𝜌𝑑𝑧) 𝜕(𝑉𝐴𝜌)𝑑𝑧
= 𝑣𝐴𝜌 − (𝑣𝐴𝜌 + ) (7)
𝜕𝑡 𝜕𝑧

𝜕(𝐴𝜌𝑑𝑧) 𝜕(𝑉𝐴𝜌)𝑑𝑧
=( )
𝜕𝑡 𝜕𝑧

𝜕(𝜌) 𝜕(𝑉𝜌)
=( ) (8)
𝜕𝑡 𝜕𝑧

B. COMPONENT CONTINUITY EQUATIONS (COMPONENT BALANCES).

Unlike mass, chemical components are not conserved. If a reaction occurs inside a system, the
number of moles of an individual component will increase if it is a product of the reaction or
decrease if it is a reactant. Therefore the component continuity equation of the jth chemical species
of the system says
𝐹𝑙𝑜𝑤 𝑜𝑓 𝑗𝑡ℎ 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 − 𝐹𝑙𝑜𝑤 𝑜𝑓 𝑗𝑡ℎ 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑜𝑢𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
+ 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑗𝑡ℎ 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑓𝑟𝑜𝑚 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠
= 𝑡𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑗𝑡ℎ 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛𝑠𝑖𝑑𝑒 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
Units: Moles of j component per time
Example 2.3. Consider the same tank of perfectly mixed liquid that we used in Example 2.1
except that a chemical reaction takes place in the liquid in the tank. The system is now a CSTR
(continuous stirred-tank reactor) as shown in Fig. 2.3. Component A reacts irreversibly and at a
specific reaction rate k to form product, component B. A→B
Let the concentration of component A in the inflowing feed stream be (moles of A per unit
volume) and in the reactor CA. Assuming a simple first-order reaction, the rate of consumption of
reactant A per unit volume will be directly proportional to the instantaneous concentration of A in
the tank.
𝐹𝑙𝑜𝑤 𝑜𝑓 𝐴 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐹0 𝐶𝐴0
𝐹𝑙𝑜𝑤 𝑜𝑓 𝐴 𝑜𝑢𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐹𝐶𝐴
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝐴 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − 𝑉𝑘𝐶𝐴
𝑑(𝑉𝐶𝐴 )
𝑡𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝐴 𝑖𝑛𝑠𝑖𝑑𝑒 𝑡𝑎𝑛𝑘 =
𝑑𝑡

Combining all these above equations

𝑑(𝑉𝐶𝐴 )
= 𝐹0 𝐶𝐴0 − 𝐹𝐶𝐴 − 𝑉𝑘𝐶𝐴
𝑑𝑡

Similarly for component B

𝑑(𝑉𝐶𝐵)
= 𝐹0 𝐶𝐵0 − 𝐹𝐶𝐵 + 𝑉𝑘𝐶𝐵
𝑑𝑡

𝑀𝐴 𝐶𝐴 + 𝑀𝐵 𝐶𝐵 = 𝜌
Example 2.4. Suppose we have the same macroscopic system as above except that now
consecutive reactions occur. Reactant A goes to B at a specific reaction rate k1 but B can react at a
specific reaction rate k2 to form a third component C.
A→B→C
Assuming first-order reactions, the component continuity equations for components A, B, and C
are
𝑑(𝑉𝐶𝐴 )
= 𝐹0 𝐶𝐴0 − 𝐹𝐶𝐴 − 𝑉𝑘1 𝐶𝐴
𝑑𝑡

𝑑(𝑉𝐶𝐵)
𝑑𝑡
= 𝐹0 𝐶𝐵0 − 𝐹𝐶𝐵 + 𝑉𝑘1 𝐶𝐴 − 𝑉𝑘2 𝐶𝐵
𝑑(𝑉𝐶𝐶 )
= 𝐹0 𝐶𝐶0 − 𝐹𝐶𝐶 + 𝑉𝑘2 𝐶𝐵
𝑑𝑡

The component concentrations are related to the density

∑𝐶𝑗=𝐴(𝑀𝑗 𝐶𝑗 ) = 0
Example 2.5. Instead of fluid flowing down a pipe as in Example 2.2, suppose the pipe is a
tubular reactor in which the same reaction A → B of Example 2.3 takes place. As a slice of
material moves down the length of the reactor the concentration of reactant CA decreases as A is
consumed. Density ρ, velocity v, and concentration CA can all vary with time and axial position z.
We still assume plug-flow conditions so that there are no radial gradients in velocity, density, or
concentration. Develop a mathematical expression.

Solution:
The concentration of A fed to the inlet of the reactor at z = 0 is defined as
𝐶𝐴(𝑡,0) = 𝐶𝐴0(𝑡)
The concentration of A in the reactor effluent at z = L is defined as
𝐶𝐴(𝑡,𝐿) = 𝐶𝐴𝐿(𝑡)
apply the component continuity equation for reactant A to a small differential slice of
width dz, as shown in Fig. 2.4.

The inflow terms can be split into two types: bulk flow and diffusion. Diffusion can occur
because of the concentration gradient in the axial direction

𝜕𝐶𝐴
𝑁𝐴 = −𝐷𝐴
𝜕𝑧

Where 𝐷𝐴 is a diffusion coefficient due to both diffusion and turbulence in the fluid flow (so-
called “eddy diffusivity”). 𝐷𝐴 has units of length’ per unit time.

Molar flow of A into boundary at z (bulk flow and diffusion)= 𝑉𝐴𝐶𝐴 + 𝐴𝑁𝐴
𝜕(𝑉𝐴𝐶𝐴 +𝐴𝑁𝐴)
Molar flow of A leaving system at boundary z + dz = 𝑉𝐴𝐶𝐴 + 𝐴𝑁𝐴 + 𝜕𝑧
𝑑𝑧
Rate of formation of A inside system= −𝑘𝐶𝐴 𝐴𝑑𝑧
𝜕(𝐴𝑑𝑧𝐶𝐴)
Time rate of change of A inside system =
𝜕𝑡
From component balance equation
𝜕(𝐴𝑑𝑧𝐶𝐴 ) 𝜕(𝑉𝐴𝐶𝐴 +𝐴𝑁𝐴)
= 𝑉𝐴𝐶𝐴 + 𝐴𝑁𝐴 − (𝑉𝐴𝐶𝐴 + 𝐴𝑁𝐴 + 𝑑𝑧)−𝑘𝐶𝐴 𝐴𝑑𝑧
𝜕𝑡 𝜕𝑧
𝜕(𝐴𝑑𝑧𝐶𝐴 ) 𝜕(𝑉𝐴𝐶𝐴 +𝐴𝑁𝐴 )
𝜕𝑡
=− 𝜕𝑧
𝑑𝑧)−𝑘𝐶𝐴 𝐴𝑑𝑧
𝜕(𝐶𝐴 ) 𝜕(𝑉𝐶𝐴 +𝑁𝐴 )
𝜕𝑡
=− 𝜕𝑧
−𝑘𝐶𝐴
𝜕(𝐶𝐴 ) 𝜕(𝑉𝐶𝐴 ) 𝜕(𝑁𝐴 )
𝜕𝑡
=− 𝜕𝑧
−− 𝜕𝑧
−𝑘𝐶𝐴
𝜕𝐶𝐴
𝜕(𝐶𝐴 ) 𝜕(𝑉𝐶𝐴 ) 𝜕(−𝐷𝐴 )
𝜕𝑧
=− −− −𝑘𝐶𝐴
𝜕𝑡 𝜕𝑧 𝜕𝑧
𝜕𝐶
𝜕(𝐶𝐴 ) 𝜕(𝑉𝐶𝐴 ) 𝜕(𝐷𝐴 𝜕𝑧𝐴 )
𝜕𝑡
=− 𝜕𝑧
+ 𝜕𝑧
−𝑘𝐶
𝐴
𝜕𝐶𝐴
𝜕(𝐶𝐴 ) 𝜕(𝑉𝐶 ) 𝜕(𝐷𝐴 )
𝜕𝑡
+ 𝜕𝑧 𝐴 + 𝑘𝐶𝐴 = 𝜕𝑧
𝜕𝑧

The units of the equation are moles A per volume per time.

z=0 z=z z=z+dz z=L

Energy Equation
The first law of thermodynamics puts forward the principle of conservation of energy. Written for
a general “open” system

Flow of internal, kinetic, and potential energy into system by convection or diffusion- Flow of
internal, kinetic, and potential energy out of system by convection or diffusion+ heat added to
system by conduction, radiation, and reaction - work done by system on surroundings (shaft work
and PV work)= time rate of change of internal, kinetic, and potential energy inside system

Example 2.6. The CSTR system of Example 2.3 will be considered again, this time with a cooling
coil inside the tank that can remove the exothermic heat of reaction λ (Btu/lb . mol of A reacted or
Cal/g. mol of A reacted). We use the normal convention that λ is negative for an exothermic
reaction and positive for an endothermic reaction.

The rate of heat generation (energy per time) due to reaction is the rate of consumption of A times
λ.

𝑄𝐺 = −𝜆𝑉𝐶𝐴 𝑘
The rate of heat removal from the reaction mass to the cooling coil is -Q (energy per time). The
temperature of the feed stream is T0 and the temperature in the reactor is T (0R or K).
Writing energy equation for this system
𝑑((𝑈+𝐾+∅)𝑉𝜌)
𝐹0 𝜌0 (𝑈0 + 𝐾0 + ∅0 ) − 𝐹𝜌(𝑈 + 𝐾 + ∅) + (𝑄𝐺 + 𝑄) − (𝑊 + 𝐹𝑃 − 𝐹0 𝑃0 ) = 𝑑𝑡

Where
U = internal energy (energy per unit mass)
K = kinetic energy (energy per unit mass)
φ = potential energy (energy per unit mass)
W = shaft work done by system (energy per time)
P = pressure of system
P0 = pressure of feed stream
 F
CA
ρ
T

𝑑((𝑈)𝑉𝜌)
𝑑𝑡
= 𝐹0 𝜌0 𝑈0 − 𝐹𝜌𝑈 + (𝑄𝐺 + 𝑄) − (𝐹𝑃 − 𝐹0 𝑃0 )
𝑑((𝑈)𝑉𝜌) 𝑃 𝑃
𝑑𝑡
= 𝐹0 𝜌0 𝑈0 − 𝐹𝜌𝑈 + (𝑄𝐺 + 𝑄) − (𝐹𝜌 𝜌 − 𝐹0 𝜌0 𝜌0 )
0
𝑑((𝑈)𝑉𝜌) 𝑃0 𝑃
𝑑𝑡
= 𝐹0 𝜌0 𝑈0 + 𝐹0 𝜌0 𝜌 − 𝐹𝜌𝑈 − 𝐹𝜌 𝜌 + (𝑄𝐺 + 𝑄)
0
𝑑((𝑈)𝑉𝜌) 𝑃0 𝑃
= 𝐹0 𝜌0 (𝑈0 + 𝜌 ) − 𝐹𝜌 (𝑈 + 𝜌) + 𝑄𝐺 + 𝑄
𝑑𝑡 0
𝑑((𝑈)𝑉𝜌)
= 𝐹0 𝜌0 (𝑈0 + 𝑃0 𝑉0 ) − 𝐹𝜌(𝑈 + 𝑃𝑉) + 𝑄𝐺 + 𝑄
𝑑𝑡

where V is the specific volume (ft3/lb, or m3/kg), the reciprocal of the density.
Enthalpy, H or h, is defined: H=U+PV
𝑑((𝑈)𝑉𝜌)
𝑑𝑡
= 𝐹0 𝜌0 ℎ0 − 𝐹𝜌ℎ + 𝑄 − 𝜆𝑉𝐶𝐴 𝑘
For liquids the PV term is negligible compared to the U term, and we use the time rate of change
of the enthalpy of the system instead of the internal energy of the system.

𝑑(𝑉𝜌ℎ)
𝑑𝑡
= 𝐹0 𝜌0 ℎ0 − 𝐹𝜌ℎ + 𝑄 − 𝜆𝑉𝐶𝐴 𝑘

𝜕𝐻 𝜕𝑈
𝐶𝑃 = ( 𝜕𝑇 ) & 𝐶𝑉 = (𝜕𝑇 )
𝑃 𝑉
h = 𝐶𝑃 𝑇

𝜌𝐶𝑃 𝑑(𝑉𝑇)
= 𝜌𝐶𝑃 (𝐹0 𝑇0 − 𝐹𝑇) + 𝑄 − 𝜆𝑉𝐶𝐴 𝑘
𝑑𝑡
 FV

TV
Example 2.7.
y

ρv
Vv, P, ρv, Tv, y
FA0

CA0
VL, CA, ρ, T F
ρ0
CA
T0
ρ

To show what form the energy equation takes for a two-phase system, consider the
CSTR process shown in Fig. 2.6. Both a liquid product stream F and a vapor
product stream Fv (volumetric flow) are withdrawn from the vessel. The pressure in
the reactor is P. Vapor and liquid volumes are Vv and V. The density and
temperature of the vapor phase are ρv and Tv. The mole fraction of A in the vapor is
y. If the phases are in thermal equilibrium, the vapor and liquid temperatures are
equal (T = Tv ). If the phases are in phase equilibrium, the liquid and vapor
compositions are related by Raoult’s law, a relative volatility relationship or some
other vapor-liquid equilibrium relationship. The enthalpy of the vapour phase H or
is a function of composition y, temperature Tv and pressure P. Neglecting kinetic-
energy and potential-energy terms and the work term, and replacing internal
energies with enthalpies in the time derivative, the energy equation of the system
(the vapor and liquid contents of the tank) becomes

𝑑(𝜌𝑉𝐿 ℎ+𝜌𝑣 𝑉𝑣 𝐻)
𝑑𝑡
= 𝐹0 𝜌0 ℎ0 − 𝐹𝜌ℎ − 𝐹𝑣 𝜌𝑣 ℎ𝑣 + 𝑄 − 𝜆𝑉𝐶𝐴 𝑘

For liquids, enthalpy change is h = 𝐶𝑃 𝑇

For Vapours , enthalpy change is H = 𝐶𝑃 𝑇 + 𝜆𝑣

𝑑(𝜌𝑉𝐿 ℎ+𝜌𝑣 𝑉𝑣 (𝐶𝑃 𝑇+𝜆𝑣 ))

= 𝐹0 𝜌0 𝐶𝑃 𝑇0 − 𝐹𝜌𝐶𝑃 𝑇 − 𝐹𝑣 𝜌𝑣 (𝐶𝑃 𝑇 + 𝜆𝑣 ) + 𝑄 − 𝜆𝑉𝐶𝐴 𝑘
𝑑𝑡

Example 2.8.
To illustrate the application of the energy equation to a microscopic system, let us return to the
plug-flow tubular reactor and now keep track of temperature changes as the fluid flows down the
pipe. We will again assume no radial gradients in velocity, concentration, or temperature (a very
poor assumption in some strongly exothermic systems if the pipe diameter is not kept small).
Suppose that the reactor has a cooling jacket around it as shown in Fig. 2.7. Heat can be
transferred from the process fluid reactants and products at the metal wall of the reactor at
temperature The heat is subsequently transferred to the cooling water. For a complete description
of the system we would need energy equations for the process fluid, the metal wall, and the
cooling water. Here we will concern ourselves only with the process energy equation. Looking at a
little slice of the process fluid as our system, we can derive each of the terms of Eq. (2.18).
Potential-energy and kinetic-energy terms are assumed negligible, and there is no work term. The
simplified forms of the internal energy and enthalpy are assumed. Diffusive flow is assumed
negligible compared to bulk flow. We will include the possibility for conduction of heat axially
along the reactor due to molecular or turbulent conduction.

Flow of energy (enthalpy) into boundary at z due to bulk flow: 𝑣𝐴𝜌𝐶𝑃 𝑇

𝜕(𝑣𝐴𝜌𝐶𝑃 𝑇 )
Flow of energy (enthalpy) out of boundary at z + dz: 𝑣𝐴𝜌𝐶𝑃 𝑇 + 𝜕𝑍
𝑑𝑧
Heat generated by chemical reaction: −𝐴𝑑𝑧𝑘𝐶𝐴 𝜆
Heat transferred to metal wall: −ℎ 𝑇 𝜋𝐷 𝑑𝑧(𝑇 − 𝑇𝑀 )
where ℎ 𝑇 = heat transfer film coefficient,
D= diameter of pipe,
Heat conduction into boundary at z: 𝑞𝑧 𝐴
where 𝑞𝑧 is a heat flux in the z direction due to conduction. We will use Fourier’s law to express
in terms of a temperature driving force:

𝜕𝑇
𝑞𝑧 = −𝑘 𝑇 𝜕𝑧
where 𝑘 𝑇 is an effective thermal conductivity
𝜕(𝑞𝑧 𝐴)
Heat conduction out of boundary at z + dz: 𝑞𝑧 𝐴 + 𝑑𝑧
𝜕𝑧
𝜕(𝜌𝐴𝑑𝑧𝐶𝑃 𝑇)
Rate of change of internal energy (enthalpy) of the system:
𝜕𝑡
Combining all the above gives

𝜕(𝜌𝐴𝑑𝑧𝐶𝑃 𝑇) 𝜕(𝑣𝐴𝜌𝐶𝑃 𝑇 )
= 𝑣𝐴𝜌𝐶𝑃 𝑇 − (𝑣𝐴𝜌𝐶𝑃 𝑇 + 𝑑𝑧 ) − 𝐴𝑑𝑧𝑘𝐶𝐴 𝜆 − ℎ 𝑇 𝜋𝐷 𝑑𝑧(𝑇 − 𝑇𝑀 )
𝜕𝑡 𝜕𝑍
𝜕(𝑞𝑧 𝐴)
+ 𝑞𝑧 𝐴 − (𝑞𝑧 𝐴 + 𝑑𝑧 )
𝜕𝑧
Divide above equation by Adz.

ℎ𝑇 𝜋𝐷 𝑑𝑧
ℎ 𝑇 𝜋𝐷 𝑑𝑧 =
𝐴𝑑𝑧
= ℎ𝑇𝜋𝐷𝜋𝐷
2
𝑑𝑧
= 4ℎ𝐷𝑇
4
𝑑𝑧
𝜕𝑇
𝜕(𝜌𝐶𝑃 𝑇) 𝜕(𝑣𝜌𝐶𝑃 𝑇 ) 4ℎ𝑇 𝜕(𝑘𝑇 )
𝜕𝑧
+ + 𝑘𝐶𝐴 𝜆 − (𝑇 − 𝑇𝑀 ) =
𝜕𝑡 𝜕𝑍 𝐷 𝜕𝑧
Equation of motion
Example 2.10. Probably the best contemporary example of a variable-mass system would be the
equations of motion for a space rocket whose mass decreases as fuel is consumed. However, to
stick with chemical engineering systems, let us consider the problem sketched in Fig. 2.8.
Petroleum pipelines are sometimes used for transferring several products from one location to
another on a batch basis, i.e., one product at a time. To reduce product contamination at the end of
a batch transfer, a leather ball or “pig” that just fits the pipe is inserted in one end of the line. Inert
gas is introduced behind the pig to push it through the line, thus purging the line of whatever
liquid is in it. To write a force balance on the liquid still in the pipe as it is pushed out, we must
take into account the changing mass of material. Assume the pig is weightless and frictionless
compared with the liquid in the line. Let z be the axial position of the pig at any time. The liquid is
incompressible (density and flows in plug flow. It exerts a frictional force proportional to the
square of its velocity and to the length of pipe still containing liquid.

𝐹𝑟𝑖𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑓𝑜𝑟𝑐𝑒 = 𝐾𝐹 (𝐿 − 𝑍)𝑣 2

The cross-sectional area of the pipe is A
The mass of fluid in the pipe is = (𝐿 − 𝑧)𝐴𝑃 𝜌
The pressure P0 of inert gas behind the pig is essentially constant all the way down the pipeline.
The tank into which the liquid dumps is at atmospheric pressure. The pipeline is horizontal. A
force balance in the horizontal z direction yields
𝑑(𝑣(𝐿−𝑧)𝐴𝑃𝜌 )
𝑑𝑡
= 𝑃0 𝐴𝑝 − 𝐾𝐹 (𝐿 − 𝑍)𝑣 2
𝑑𝑧
𝑣 = 𝑑𝑡
Substitute above equation in balanced equation
𝑑𝑧
𝑑( 𝑑𝑡 (𝐿−𝑧)𝐴𝑃𝜌 ) 𝑑𝑧 2
= 𝑃0 𝐴𝑝 − 𝐾𝐹 (𝐿 − 𝑍) ( 𝑑𝑡 )
𝑑𝑡
Example 2.11. As an example of a force balance for a microscopic system, let us look at the
classic problem of the laminar flow of an incompressible, newtonian liquid in a cylindrical pipe.
By “newtonian” we mean that its shear force (resistance that adjacent layers of fluid exhibit to
flowing past each other) is proportional to the shear rate or the velocity gradient.
𝜕𝑉
𝜏𝑟𝑧 = −𝜇 𝑧
𝜕𝑟
a small, doughnut-shaped element, half of which is shown in Fig. 2.9. Since the fluid is
incompressible there is no radial flow of fluid, or vr= 0. The system is symmetrical with respect to
the angular coordinate (around the circumference of the pipe), and therefore we need consider
only the two dimensions r and z. The forces in the z direction acting on the element are

Forces acting left to right:

Shear force on face at r = r; 𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧)
Pressure force on face at z = 𝑧; (2𝜋𝑟𝑑𝑟)𝑃
Forces acting right to left ∶
𝜕(𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧))𝑑𝑧
Shear force on face at r = r + dr; 𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧) +
𝜕𝑧
𝜕((2𝜋𝑟𝑑𝑟)𝑃)𝑑𝑧
Pressure force on face at z = z + dz; (2𝜋𝑟𝑑𝑟)𝑃 + 𝜕𝑧
𝜕(2𝜋𝑟𝑑𝑟𝑑𝑧𝜌𝑣𝑧 )
The rate of change of of the system is 𝜕𝑡
Combining all the above gives

𝜕(2𝜋𝑟𝑑𝑟𝑑𝑧𝜌𝑣𝑧 ) 𝜕(𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧))𝑑𝑧

= 𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧) − (𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧) + ) + (2𝜋𝑟𝑑𝑟)𝑃 − ((2𝜋𝑟𝑑𝑟)𝑃 +
𝜕𝑡 𝜕𝑧

𝜕((2𝜋𝑟𝑑𝑟)𝑃)𝑑𝑧
𝜕𝑧
)

𝜕(2𝜋𝑟𝑑𝑟𝑑𝑧𝜌𝑣𝑧 ) 𝜕(𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧))𝑑𝑧 𝜕((2𝜋𝑟𝑑𝑟)𝑃)𝑑𝑧

𝜕𝑡
= − 𝜕𝑧
− 𝜕𝑧
𝜕(2𝜋𝑟𝑑𝑟𝑑𝑧𝜌𝑣𝑧 ) 𝜕(𝜏𝑟𝑧 (2𝜋𝑟𝑑𝑧))𝑑𝑧 𝜕((2𝜋𝑟𝑑𝑟)𝑃)𝑑𝑧
+ + =0
𝜕𝑡 𝜕𝑧 𝜕𝑧
Transport Equations