FUNDAMENTAL LAWS

Continuity Equations
1)TOTAL CONTINUITY EQUATION (MASS BALANCE).

The principle of the conservation of mass when applied to a dynamic system says

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓

{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = { }− { } (Unit: Mass/time)
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
➢ One total continuity equation is required for One system
➢ The Accumulation term will be partial of total derivative.
𝑑
➢ Total derivative ( ) ➔ for Lumped parameter system OR Macroscopic system
𝑑𝑡
Ex: CSTR
𝜕
➢ Partial derivative (𝜕𝑡) ➔ for distributed parameter system OR Microscopic System
Ex: PFR
Problem 1
Macroscopic System

Consider the tank of perfectly mixed liquid into which flows a liquid stream at a volumetric
rate of Fo, (m3/min) and with a density of ρ (kg/m3). The volumetric holdup of liquid in the
tank is V (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
Solution:
➢ Macroscopic system means definite and finite size.
➢ The mass balance is around the whole tank
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = { }− { } ----(1) (Unit: Mass/time)
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑚3 𝐾𝑔 𝐾𝑔
{ } = 𝐹𝑜 𝜌𝑜 𝐶ℎ𝑒𝑐𝑘 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡𝑠 ∶ × 3 =
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑠𝑒𝑐 𝑚 𝑠𝑒𝑐
 𝑅𝑎𝑡𝑒 𝑜𝑓
{ } = F𝜌
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡

𝑅𝑎𝑡𝑒 𝑜𝑓 𝐾𝑔 3
𝑑(𝜌𝑉) 𝑚 3×𝑚 𝐾𝑔
{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = 𝐶ℎ𝑒𝑐𝑘 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡𝑠: =
𝑑𝑡 𝑠𝑒𝑐 𝑠𝑒𝑐
𝑀𝑎𝑠𝑠
Sub. all in eqn.(1)
𝑑(𝜌𝑉)
= 𝐹𝑜 𝜌𝑜 − F𝜌 Model equation for the tank
𝑑𝑡

Problem 2
Microscopic system
Fluid is flowing through a constant-diameter cylindrical pipe. 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.

Solution

➢ There are now two independent variables: time t and position z.

➢ Density and velocity are functions of both t and z
A = Cross section area of slice
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = {𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛} − {𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡} ----(1) (Unit: Mass/time)
𝑀𝑎𝑠𝑠 𝑎𝑡 𝑍 𝑎𝑡 𝑍 + 𝑑𝑍

𝑅𝑎𝑡𝑒 𝑜𝑓
𝜕(𝜌𝐴𝑑𝑍)
{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = 𝜕𝑡 − − − − − −(2) 𝐻𝑒𝑟𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 = 𝐴 × 𝑑𝑧
𝑀𝑎𝑠𝑠
𝑅𝑎𝑡𝑒 𝑜𝑓
{ } = 𝜌𝐴𝑣 − − − − − (3) 𝑤ℎ𝑒𝑟𝑒 𝑣 = 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑎𝑡 𝑍
 𝑅𝑎𝑡𝑒 𝑜𝑓
{𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡} =
𝑎𝑡 𝑍 + 𝑑𝑍
Using Taylor Series expansion for any function f(Z) around Z i.e. Z+ dZ

𝟏 𝝏𝒇 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝒇𝒁 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Here the function is fZ = (ρAv)
𝟏 𝝏(ρAv) 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = ρAv + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Note: Where dZ is small and (dZ)2 is very small hence second term in above equation is neglected.
𝟏 𝝏(ρAv)
𝒇𝒁+𝒅𝒁 = ρAv + 𝟏! 𝝏𝒁
𝒅𝒁 ----------- (4)

Substituting Eqn.(2), (3),(4) in Eqn.(1) we get

𝜕(𝜌𝐴𝑑𝑍) 1 𝜕(ρAv)
= 𝜌𝐴𝑣 − (ρAv + 𝑑𝑍)
𝜕𝑡 1! 𝜕𝑍
Dividing by Adz
𝜕(𝜌) 𝜕(ρv)
= 𝜌𝐴𝑣 − ρAv −
𝜕𝑡 𝜕𝑍
𝜕(𝜌) 𝜕(ρv)
+ =0
𝜕𝑡 𝜕𝑍
COMPONENT CONTINUITY EQUATIONS
(COMPONENT BALANCES).
Note: 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

Rate of Rate of flow Rate of flow Rate of Rate of

{ Accumulation of } = {of species i in −
} { of species i in +
} {Generation −
} {consumption }
species i to the system to the system of species i of species i

➢ Unit: Moles/time
➢ Flow can be convective( or bulk flow) or molecular flow( diffusion flow)
➢ If N = No. of components, then N component continuity equation can be written.
However one total mass balance and N component balance are not all independent.
Since sum of all these moles multiplied by their respective molecular weight equals
total mass.
➢ Therefor we use total mass balance and (N-1) component balance equations to get a
solution.
Problem 3:
Macroscopic system
Consider the same tank of perfectly mixed liquid that we used in Problem 1, except that a
chemical reaction takes place in the liquid in the tank. The system is now a CSTR (continuous
stirred-tank reactor) .Component A reacts irreversibly and at a specific reaction rate k to form
product, component B.
K
A➔B
Solution:

Rate of Rate of flow Rate of flow Rate of Rate of

{Accumulation of } = {of species i in } − {of species i out } + {Generation } − {consumption } − −(1)
species i to the system to the system of species i of species i

Component A balance
Rate of flow 𝑚3 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙𝑒𝑠
{of species i in } = 𝐹𝑜 𝐶𝐴𝑂 𝑐ℎ𝑒𝑐𝑘𝑖𝑛𝑔 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡𝑠 ∶ × 3
=
to the system 𝑠𝑒𝑐 𝑚 𝑠𝑒𝑐

Rate of flow
{of species i in } = 𝐹𝐶𝐴
to the system

Rate of 1 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙𝑒𝑠

{consumption } = (−𝑟𝐴 )𝑉 = −𝐾𝐶𝐴 𝑉 𝐶ℎ𝑒𝑐𝑘𝑖𝑛𝑔 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 ∶ × 3
× 𝑚3 =
of species i 𝑠𝑒𝑐 𝑚 𝑠𝑒𝑐

Rate of 𝑑(𝐶𝐴 𝑉)
{Accumulation of } =
species i 𝑑𝑡

Substituting all the terms of component A balance in eqn.(1)

𝑑(𝐶𝐴 𝑉)
= 𝐹𝑜 𝐶𝐴𝑂 − 𝐹𝐶𝐴 − 𝐾𝐶𝐴 𝑉
𝑑𝑡
Component B balance
𝑑(𝐶𝐵 𝑉)
= 𝐹𝑜 𝐶𝐵𝑂 − 𝐹𝐶𝐵 + 𝐾𝐶𝐴 𝑉
𝑑𝑡
‘+’, Since B is generated
Total Continuity Equation

Since CA , CB , and ρ are uniquely related by

𝐾𝑔 𝐾𝑔𝑚𝑜𝑙𝑒 𝐾𝑔 𝐾𝑔𝑚𝑜𝑙𝑒 𝐾𝑔
𝑀𝐴 𝐶𝐴 + 𝑀𝐵 𝐶𝐵 = 𝜌 Checking of units: × + 𝐾𝑔𝑚𝑜𝑙𝑒 × =
𝐾𝑔𝑚𝑜𝑙𝑒 𝑉𝑜𝑙 𝑉𝑜𝑙 𝑣𝑜𝑙𝑢𝑚𝑒

Problem 4
Microscopic system

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.
K1 K2
A➔ B➔ C
Assuming first-order reactions. Derive the model.

Solutions:

The component continuity equations for components A, B, and C are

𝑑(𝐶𝐴 𝑉)
= 𝐹𝑜 𝐶𝐴𝑂 − 𝐹𝐶𝐴 − 𝐾1 𝐶𝐴 𝑉
𝑑𝑡

𝑑(𝐶𝐵 𝑉)
= 𝐹𝑜 𝐶𝐵𝑂 − 𝐹𝐶𝐵 + 𝐾1 𝐶𝐴 𝑉 − 𝐾2 𝐶𝐵 𝑉
𝑑𝑡

𝑑(𝐶𝐶 𝑉)
= 𝐹𝑜 𝐶𝐶𝑂 − 𝐹𝐶𝐶 + 𝐾2 𝐶𝐵 𝑉
𝑑𝑡

Total Balance equation

𝑀𝐴 𝐶𝐴 + 𝑀𝐵 𝐶𝐵 + 𝑀𝐶 𝐶𝐶 = 𝜌
Note: There are 3 component (variable) and 4 equations Therefore DOF = negative. To make
DOF zero we have to take Total balance equation and 2 component equation.
Problem 5
Microscopic System

Instead of fluid flowing down a pipe as in Problem 2 , suppose the pipe is a tubular reactor in
which the same reaction A ➔ B 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. Assume plug-flow conditions
so that there are no radial gradients in velocity, density, or concentration.

Solution:

𝑎𝑡 𝑍 = 0; 𝐶𝐴 (𝑡, 𝑍) = 𝐶𝐴 (𝑡, 0) → 𝐶𝐴𝑂 (𝑡)

𝑎𝑡 𝑍 = 𝐿; 𝐶𝐴 (𝑡, 𝑍) = 𝐶𝐴 (𝑡, 𝐿) → 𝐶𝐴𝐿 (𝑡)

Applying the component continuity equation for reactant A to a small differential slice of
width dz, as shown in Figure.
➢ The inflow term can be split into 2 types (i) Bulk flow (ii) Diffusion flow
➢ Diffusion occurs because of conc. Gradient in axial direction
➢ Diffusion is less important than bulk flow in most practical systems.

• Diffusive flux of A is given by

𝑑𝐶 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴
𝑁𝐴 = −𝐷𝐴 𝑑𝑍𝐴 𝑈𝑛𝑖𝑡𝑠: 𝑚2 𝑠𝑒𝑐
• Bulk flow of A = VCA

Rate of Rate of flow Rate of flow Rate of Rate of

{Accumulation of } = {of species i in } − {of species i out } + {Generation } − {consumption }---- (1)
species i at Z 𝑜𝑓 𝑍 + 𝑑𝑍 of species i of species i

Rate of flow
{of species A in } = (𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 ) -------- (2)
at Z
Rate of flow
{of species A out } = (𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 )𝑍+𝑑𝑍
𝑜𝑓 𝑍 + 𝑑𝑍
Using Taylor Series expansion for any function f(Z) around Z i.e. Z+ dZ

𝟏 𝝏𝒇 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝒇𝒁 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
 Here the function is fZ = (𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴)
𝟏 𝝏(𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 ) 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Note: Where dZ is small and (dZ)2 is very small hence second term in above equation is neglected.
𝟏 𝝏(𝐴𝑁𝐴 +𝑉𝐴𝐶𝐴 v)
𝒇𝒁+𝒅𝒁 = 𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 + 𝟏! 𝝏𝒁
𝒅𝒁 ----------- (3)
𝑅𝑎𝑡𝑒 𝑜𝑓
𝜕(𝐴𝐶𝐴 𝑑𝑍)
{𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 } = 𝜕𝑡
− − − − − −(4) 𝐻𝑒𝑟𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 = 𝐴 × 𝑑𝑧
𝑀𝑎𝑠𝑠

Rate of
{consumption } = −𝐾𝐶𝐴 𝐴𝑑𝑍 --------- (5)
of species A
Substituting Eqn.(2), (3),(4), (5) in Eqn.(1) we get

𝜕(𝐴𝐶𝐴 𝑑𝑍) 𝟏 𝝏(𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 )

= (𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 ) − 𝐴𝑁𝐴 + 𝑉𝐴𝐶𝐴 + 𝒅𝒁 − 𝐾𝐶𝐴 𝐴𝑑𝑍
𝜕𝑡 𝟏! 𝝏𝒁
Dividing AdZ

𝜕(𝐶𝐴 ) 𝝏(𝑁𝐴 + 𝑉𝐶𝐴 )

= − 𝐾𝐶𝐴
𝜕𝑡 𝝏𝒁
𝜕𝐶𝐴
𝜕(𝐶𝐴 ) 𝝏(𝑉𝐶𝐴 ) 𝜕 (𝐷𝐴 )
𝜕𝑍
+ + 𝐾𝐶𝐴 =
𝜕𝑡 𝝏𝒁 𝜕𝑍
Energy Equation

𝑅𝑎𝑡𝑒 𝑜𝑓 Flow of Energy Flow of Energy

in by out by Heat added to the work done
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
[
𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦
]= convection − convection + [system by conduction] − [ by system ]
or or 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛, 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (shaft + PV)
𝑖𝑛𝑠𝑖𝑑𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 [ diffusion ] [ diffusion ]

------------ (1)

Note: 1) Units of eqn.(1) is energy/time

2) Energy = Internal energy(U)+ Kinetic energy( K) + Potential energy(Φ)
3) Velocity and elevation difference is low in most practical problems hence
negligible KE and PE.
4) U depends on not only temperature but also on mass flow and composition.
5) Shaft work is work due to agitator or stirrer.
6) PV term is pressure and volume work. This term is when the system contains
Vapour which causes expansion and compression leading to change in Volume
and Pressure.
7) Energy balance equation are almost accompanied by Mass balance equation.
Problem 6

Macroscopic system

The CSTR system of Problem 3, will be considered again, this time with a cooling coil
inside the tank that can remove the exothermic heat of reaction λ( 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 given by QG. The rate of heat removal from the reaction mass to the cooling
coil is Q (Energy/time). Let U, K and Φ be internal, Kinetic and Potential energy. W is
the shaft work done by the system. P and Po is the pressure of the system and feed stream
respectively.

Solution

Assumption: 1) Inlet and outlet velocities are low hence KE is negligible

2) Elevation of inlet and outlet flow are small hence PE is neglected
3) Stirrer ➔ W
𝑅𝑎𝑡𝑒 𝑜𝑓 Flow of Energy Flow of Energy
in by out by Heat added to the work done
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
[ ]= convection − convection + [ system by conduction ] − [ by system ]
𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦
or or 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛, 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (shaft + PV)
𝑖𝑛𝑠𝑖𝑑𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 [ diffusion ] [ diffusion ]
Flow of Energy
in by 𝑚3 𝐾𝑔 𝐸𝑛𝑒𝑟𝑔𝑦 𝐸𝑛𝑒𝑟𝑔𝑦
convection = 𝐹𝑜 𝜌𝑜 𝑈𝑜 𝐶ℎ𝑒𝑐𝑘 𝑡ℎ𝑒 𝑈𝑛𝑖𝑡𝑠: × × =
𝑠𝑒𝑐 𝑚3 𝐾𝑔 𝑡𝑖𝑚𝑒
or
[ diffusion ]
 Flow of Energy
out by
convection = 𝐹𝜌𝑈
or
[ diffusion ]

Heat added to the

[ system by ] = 𝑄𝐺 − 𝑄
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛

work done
[ by system ] = (W + FP − Fo Po )
(shaft + PV)

𝑚3 𝑁 𝑁−𝑚
𝐶ℎ𝑒𝑐𝑘 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝐹𝑃 = × 2 == = 𝐽𝑜𝑢𝑙𝑒 (𝐸𝑛𝑒𝑟𝑔𝑦)
𝑠𝑒𝑐 𝑚 𝑠𝑒𝑐

𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑑(𝑈𝜌𝑉)
[ ]=
𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦 𝑑𝑡
𝑖𝑛𝑠𝑖𝑑𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
Substituting all these terms in Eqn.(1)
𝑑(𝑈𝜌𝑉)
= 𝐹𝑜 𝜌𝑜 𝑈𝑜 − 𝐹𝜌𝑈 + 𝑄𝐺 − 𝑄 − (W + FP − Fo Po )
𝑑𝑡
Rearranging

𝑑(𝑈𝜌𝑉)
= (𝐹𝑜 𝜌𝑜 𝑈𝑜 + Fo Po ) − (𝐹𝜌𝑈 + FP) + 𝑄𝐺 − 𝑄 − W
𝑑𝑡
𝑑(𝑈𝜌𝑉) Po P
= 𝐹𝑜 𝜌𝑜 (𝑈𝑜 + ) − 𝐹𝜌 (𝑈 + ) + 𝑄𝐺 − 𝑄 − W
𝑑𝑡 𝜌𝑜 𝜌

Here Ṽ = 1/ ρ = Specific volume (Reciprocal of density)

Po
= 𝑃𝑜 Ṽ𝑜
𝜌𝑜

then

𝐹𝑜 𝜌𝑜 (𝑈𝑜 + 𝑃𝑜 Ṽ𝑜 ) = 𝐹𝑜 𝜌𝑜 ℎ𝑜 𝑊ℎ𝑒𝑟𝑒 (𝑈𝑜 + 𝑃𝑜 Ṽ𝑜 ) = ℎ𝑜 = 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦

1 moles energy energy

QG = −(K1 CA V)λ Check the units ∶ × 3
× m3 × =
sec m moles time
𝑑(𝑈𝜌𝑉)
= 𝐹𝑜 𝜌𝑜 ℎ𝑜 − 𝐹𝜌ℎ + (K1 CA V)λ − 𝑄 − W
𝑑𝑡
Problem 7

Microscopic System

Consider the same PFR given in Problem 6. Here the temperature changes as the fluid
flows down the pipe. Assume no radial gradients in velocity, concentration or
temperature. The reactor has a cooling jacket around it. Heat can be transferred from
the process fluid reactant and product at temp. T to the metal wall of the reactor at temp.
TM. The heat is subsequently transferred to the cooling water. Assume diffusion flow to
be present. Kinetic and Potential energy is considered as negligible.

Solution:
 𝑅𝑎𝑡𝑒 𝑜𝑓 Flow of Energy Flow of Energy
in by out by Heat added to the work done
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
[ ]= convection − convection + [system by conduction] − [ by system ]
𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦
or or 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛, 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (shaft + PV)
𝑖𝑛𝑠𝑖𝑑𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 [ diffusion ] [ diffusion ]

𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝜕(𝜌𝐴𝑑𝑍𝐶𝑃 𝑇)
{ }= − − − − − −(2) 𝐻𝑒𝑟𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 = 𝐴 × 𝑑𝑧
𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛 𝑡ℎ𝑒 𝜕𝑡
𝑠𝑦𝑠𝑡𝑒𝑚
𝑅𝑎𝑡𝑒 𝑜𝑓
{ } = 𝜌𝐴𝑣𝐶𝑃 𝑇 − − − − − (3) 𝑤ℎ𝑒𝑟𝑒 𝑣 = 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝐸𝑛𝑒𝑟𝑔𝑦 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑎𝑡 𝑍
𝑅𝑎𝑡𝑒 𝑜𝑓
{𝐸𝑛𝑒𝑟𝑔𝑦 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡} = (𝜌𝐴𝑣𝐶𝑃 𝑇)𝑍+𝑑𝑍
𝑎𝑡 𝑍 + 𝑑𝑍
Using Taylor Series expansion for any function f(Z) around Z i.e. Z+ dZ

𝟏 𝝏𝒇 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝒇𝒁 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Here the function is fZ = (𝜌𝐴𝑣𝐶𝑃 𝑇)
𝟏 𝝏(𝜌𝐴𝑣𝐶𝑃 𝑇) 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝜌𝐴𝑣𝐶𝑃 𝑇 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Note: Where dZ is small and (dZ)2 is very small hence second term in above equation is neglected.
𝟏 𝝏(𝜌𝐴𝑣𝐶𝑃 𝑇)
𝒇𝒁+𝒅𝒁 = 𝜌𝐴𝑣𝐶𝑃 𝑇 + 𝟏! 𝝏𝒁
𝒅𝒁 ----------- (4)

Note: Including the possibility for conduction of heat axially along the reactor due to molecular
or turbulent conduction.
 Rate of Heat
𝐶𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝜕𝑇
{ } = 𝑞𝑍 𝐴 = −𝐾 . 𝐴 -------- (5)
in the boundary 𝜕𝑍
at Z
Rate of Heat
𝐶𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑜𝑛
{ } = (𝑞𝑍 𝐴)𝑍+𝑑𝑍
in the boundary
at Z
Using Taylor Series expansion for any function f(Z) around Z i.e. Z+ dZ

𝟏 𝝏𝒇 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝒇𝒁 + 𝒅𝒁 + 𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁𝟐
Here the function is fZ = (𝑞𝑍 𝐴)
𝟏 𝝏(𝑞𝑍 𝐴) 𝟏 𝝏𝟐 𝒇
𝒇𝒁+𝒅𝒁 = 𝑞𝑍 𝐴 + 𝒅𝒁 + 𝟐
𝒅𝒁𝟐 + ⋯
𝟏! 𝝏𝒁 𝟐! 𝝏𝒁
Note: Where dZ is small and (dZ)2 is very small hence second term in above equation is
neglected.
∂T
∂T 𝟏 𝝏(−k∂Z 𝐴) ∂T
𝒇𝒁+𝒅𝒁 = (−k ∂Z) 𝐴 + 𝒅𝒁 Here Fourier ′ s Law , q Z = −k ∂Z ----------- (6)
𝟏! 𝝏𝒁

Rate of
{ generation } = 𝐾𝐶𝐴 𝐴𝑑𝑍𝜆 --------- (7)
of Energy due to reaction

Here heat is going out of

Heat transferred to metal wall = −h(πDdZ)(T − TM ) ( the system ) ----- (8)
hence negative

Substituting eqn. (2), (3), (4), (5), (6), (7) and (8) in Eqn.(1)
𝜕(𝜌𝐴𝑑𝑍𝐶𝑃 𝑇) 𝟏 𝝏(𝜌𝐴𝑣𝐶𝑃 𝑇) 𝜕𝑇
𝜕𝑡
= 𝜌𝐴𝑣𝐶𝑃 𝑇 − 𝜌𝐴𝑣𝐶𝑃 𝑇 + 𝟏! 𝝏𝒁
𝒅𝒁 + 𝐾𝐶𝐴 𝐴𝑑𝑍𝜆 − h(πDdZ)(T − TM ) − 𝑘 𝜕𝑍 . 𝐴
∂T
∂T 𝟏 𝝏(−k∂Z 𝐴)
+(k ∂Z) 𝐴 + 𝟏! 𝝏𝒁
𝒅𝒁

Dividing above eqn. by AdZ and Lt dZ➔0

∂T
𝜕(𝜌𝐶𝑃 𝑇) 𝝏(𝜌𝑣𝐶𝑃 𝑇) h(πD)(T − TM ) 𝝏 (−k ∂Z )
+ − 𝐾𝐶𝐴 𝜆 + 𝜋 2 =
𝜕𝑡 𝝏𝒁 𝐷 𝝏𝒁
4
𝜋
Where 𝐴 = 4 𝐷2
Finally
 ∂T
𝜕(𝜌𝐶𝑃 𝑇) 𝝏(𝜌𝑣𝐶𝑃 𝑇) 4h(T − TM ) 𝝏 (−k ∂Z )
+ − 𝐾𝐶𝐴 𝜆 + =
𝜕𝑡 𝝏𝒁 𝐷 𝝏𝒁