5 TANK MODELS

Stirred Tanks With Flow Rates A Function Of Level

A more complex and realistic tank modelling case is to consider the situation in which both input and output flow
rates are influenced by the level in the tank.
 In this case the inflow F1 passes through a fixed inlet valve from a pressure source, P 1.

 The pressure on the downstream side of the inlet valve is P 2, that is, the hydrostatic pressure in the tank at the level of
the valve. In a similar fashion, the outflow passes through a fixed valve with the hydrostatic pressure P 2 on the
upstream side discharging to pressure P 3. The flows F1 and F2 are influenced by the level Z and the pressures P 0 and
P3.

• Thus, applying the principle of conservation of mass to the system

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = −
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑𝑍
𝐴 = 𝐹1 − 𝐹2 ----- (1)
𝑑𝑡
• The flows F1 and F2 can be related to the pressure drop across each valve by applying the mechanical energy
balance across each valve.
• Assuming that any hydraulic transients are very fast compared to the volume transients in the system, so that we
can use the steady-state form of the mechanical energy balance equation,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐. 𝑜𝑓 𝑀𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑀𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙
= − + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑑𝑖𝑠𝑠𝑖𝑝𝑎𝑡𝑖𝑜𝑛
𝑀𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑜 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡 𝑜𝑓
𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦
𝐸𝑛𝑒𝑟𝑔𝑦 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
𝑉1 2 𝑃1 𝑉2 2 𝑃2
0= + 𝑔𝑍1 + − + 𝑔𝑍2 + − ℎ𝐿 − 𝑊𝑠 (2)
2 𝜌 2 𝜌

• The potential energy differences are negligible and there is no mechanical work, WS. Rearranging the above eqn.
𝑃2 −𝑃1 𝑉2 2 −𝑉1 2
+ + ℎ𝐿 = 0 -(3)
𝜌 2

• The steady-state mass balance across the valve gives

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
=
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
 𝜌1 𝑉1 𝑆1 = 𝜌2 𝑉2 𝑆2
𝑉1 𝑆1
𝑉2 = ------ (4)
𝑆2
• where S1 - upstream pipe cross-section area and S2 - the cross-section area at the throat of the valve. Combining
equations ( ) and ( ) and solving for Vl gives
∆𝑃
2 − −ℎ𝐿
𝜌
𝑉! = 𝑆1 2
--------- (5)
−1
𝑆2 2

• Letting the friction head be expressed as some fraction of the total pressure drop
∆𝑃 ∆𝑃
+ ℎ𝐿 = 𝐶1 2 ------ (6)
𝜌 𝜌
• Sub eqn (6) in equation (5) gives
2
• 𝑆1 𝑉1 = 𝐹1 = 𝐶1 𝑆1 𝑃1 − 𝑃2
𝑆1 2
−1 𝜌
𝑆2 2

𝐹1 = 𝐶𝑉1 𝑃1 − 𝑃2
• Where CV1= valve constant for the inlet valve
• Similarly
𝐹2 = 𝐶𝑉2 𝑃2 − 𝑃3
• The hydrostatic pressure P2 can be computed by application of the mechanical energy balance on the control
volume of the tank itself.
𝑃2 − 𝑃𝑜
= 𝑔𝑍
𝜌
𝑃2 = 𝑃𝑂 + 𝜌𝑔𝑍
Information flow diagram - Model 1
Information flow diagram - Model 2
Information flow diagram - Model 3
Wedge Shaped Tank
• Overall Mass Balance

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓

• 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 − 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑 𝑉𝜌
• = 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1)
𝑑𝑡

• V = volume of water/liquid in tank at any time t

1
• 𝑉 = × 𝑊 × ℎ × 𝐿 ---------- (2) Substituting eqn.(2) in eqn.(1) but both W and h keeps varying. To solve for height ,
2
we have to have a relation between W and h.

• Using similar Triangle rule(given in figure)

ℎ 𝑊 𝑊×ℎ
• = or ℎ = ------- (3)
𝐻 𝐵 𝐵

• Sub. eqn.(3) in eqn.(2)

1 𝐵
• 𝑉= × × ℎ2 × 𝐿 ------(4)
2 𝐻
• Sub eqn.(4) in eqn.(1) and separating the variable and Integrating with limits

• t= to ; h=ho

• t=t ; h= h

1 𝐵
𝑑 × ×ℎ2 ×𝐿
• 2 𝐻
= 𝐹1 − 𝐹2
𝑑𝑡

ℎ 2𝐻 𝑡
• ‫׬‬ℎ 𝑑ℎ2 = 𝐵𝐿
𝐹1 − 𝐹2 ‫𝑡𝑑 𝑡׬‬
𝑜 𝑜

2𝐻
• ℎ= 𝐵𝐿
𝐹1 − 𝐹2 𝑡 − 𝑡𝑜 + ℎ𝑜 2
 Conical Shaped Tank
Overall Mass Balance
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = −
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑 𝑉𝜌
= 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1)
𝑑𝑡
V = volume of water/liquid in tank at any time t
1
𝑉= × 𝜋 × 𝑟 2 × ℎ ---------- (2)
3
 Substituting eqn.(2) in eqn.(1) but both r and h keeps
varying.
 To solve for height, we have to have a relation
between r and h.
Using similar Triangle rule (given in Figure)
ℎ 𝑟 𝑅×ℎ
= or 𝑟 = ------- (3)
𝐻 𝑅 𝐻
Sub. eqn.(3) in eqn.(2)
1 𝑅2
𝑉= ×𝜋× × ℎ3 ------(4)
3 𝐻2
Sub eqn.(4) in eqn.(1) and separating the variable and Integrating with limits
t= to ; h=ho t=t ; h= h
1 𝑅2
𝑑 3 ×𝜋× 2 ×ℎ 3
𝐻
= 𝐹1 − 𝐹2
𝑑𝑡
ℎ 3𝐻 2 𝑡
‫׬‬ℎ 𝑑ℎ3 =
𝜋𝑅2
𝐹1 − 𝐹2 ‫𝑡𝑑 𝑡׬‬
𝑜 𝑜

3 3𝐻 2
ℎ= 𝜋𝑅2
𝐹1 − 𝐹2 𝑡 − 𝑡𝑜 + ℎ𝑜 3
 Home work
Hemishperical Tank
 Problem-1 (1/2)
A square tank 4m on a side and 10m height is filled to the brim. Tank has a 5 cm2 hole in the bottom which is suddenly opened.
Derive the dynamic model equation for the system and find the time required for draining the tank completely.

Given F = 0.62A (2gh)0.5 where A= CSA of the hole.

Solution
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 − 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠

𝑑 𝑉𝜌
= 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1) { no input}
𝑑𝑡

 Density ‘ρ’’ is assumed constant and Volume, V=A*h

 A= 4*4 =16 m2 (Square tank)
 Given F2 = 0.62A (2gh)0.5
𝑑ℎ 2
16 × = −0.62 × 𝐴 × 2×𝑔×ℎ
𝑑𝑡

𝑑ℎ 2
16 × = −0.62 × 5 × 10−4 × 2 × 9.81 × ℎ
𝑑𝑡
 Problem-1 (2/2)
𝑑ℎ 5 × 10−4 × 2.74 × ℎ
= −
𝑑𝑡 16
At t = 0 ; h =10m & t = t ; h = 0

0
dh 5 × 10−4 × 2.74 t
න = − න dt
10 h 16 0
10
t = 1.17 × 104 ×2 h 0

t= 7.38* 104 sec [ unit of time is sec due to ‘g’ which has unit of m2/sec]

t= 20.5 hr
 Problem-2 (1/3)
Water flows from a conical tank at a rate of 0.02(2+h2) m3/min. The diameter and height of the conical tank is 6m and
5m respectively. If the tank is initially full a) Derive a relationship between height and time. b) how long will it take
for 75% of water to flow out of the tank.

Solution:
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = −
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑 𝑉𝜌
= 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1) { no input}
𝑑𝑡

 Density ‘ρ’’ is assumed constant and Volume, V=A*h

1
𝑉= × 𝜋 × 𝑟 2 × ℎ ---------- (2)
3

Substituting eqn.(2) in eqn.(1) but both r and h keeps varying.

To solve for height, we have to have a relation between r and h.

ℎ 𝑟 𝑅×ℎ
Using similar Triangle rule (given below) = or 𝑟 = ------- (3)
𝐻 𝑅 𝐻
 Problem-2 (2/3)
Sub. eqn.(3) in eqn.(2)
1 𝑅2
𝑉= ×𝜋× × ℎ3 ------(4)
3 𝐻2

Given F2 = 0.02(2+h2) m3/min

To find the height corresponding to 25 % of water inside the conical Tank

1
Total volume (when conical tank is filled to brim), 𝑉 = × 𝜋 × 𝑅2 × 𝐻
3
1
V= × π × 32 × 5 = 47.1 m3
3

Volume corresponding to 25% inside the tank = 0.25 x 47.1 = 31.25 m3

1 2 1 𝑅2
i.e. 𝑉 = ×π×r ×h = ×𝜋× × ℎ3 = 11.775
3 3 𝐻2

1 32
× 𝜋 × 2 × ℎ3 = 11.775
3 5
h= 3.15 m
Relation between height and time

Using eqn(1) and eqn.(4) and F2 we get

𝟏 𝑹𝟐
𝒅 𝟑 × 𝝅 × 𝟐 × 𝒉𝟑
𝑯
= −𝟎. 𝟎𝟐 𝟐 + 𝒉𝟐
𝒅𝒕

Rearranging and integrating with limits

At t =0 ; h= 5m

At t = t ; h = 3.15 m

𝑡 3.15 ℎ2 𝑑ℎ
-‫׬‬0 𝑑𝑡 = 56.5 ‫׬‬5 2+ℎ2

113
𝑡 = −56.5ℎ + 𝑡𝑎𝑛−1 2ℎ
2
3.15
3.15 113
𝑡 = −56.5ℎ 5 + 𝑡𝑎𝑛−1 2 ℎ
2 5

113
𝑡 = −56.5 3.15 − 5 + 𝑡𝑎𝑛−14.45 − 𝑡𝑎𝑛−1 7.07
2

t= 98 min
 Problem-2 (3/3)
Relation between height and time

Using eqn(1) and eqn.(4) and F2 we get

𝟏 𝑹𝟐
𝒅 × 𝝅 × 𝟐 × 𝒉𝟑
𝟑 𝑯
= −𝟎. 𝟎𝟐 𝟐 + 𝒉𝟐
𝒅𝒕

Rearranging and integrating with limits

At t =0 ; h= 5m ; At t = t ; h = 3.15 m

𝑡 3.15 ℎ 2 𝑑ℎ
-‫׬‬0 𝑑𝑡 = 56.5 ‫׬‬5
2+ℎ 2

113
𝑡 = −56.5ℎ + 𝑡𝑎𝑛−1 2ℎ
2
3.15
3.15 113
𝑡 = −56.5ℎ 5 + 𝑡𝑎𝑛−1 2 ℎ
2 5

113
𝑡 = −56.5 3.15 − 5 + 𝑡𝑎𝑛−1 4.45 − 𝑡𝑎𝑛−1 7.07
2

t= 98 min
Flow rate at t = 98 min and h=3.15 m

F2 = 0.02(2+3.152) m3/min

F2= 0.24 m3/min

Home Work

Water flows from a conical tank at a rate of 0.02(2+h)2 m3/min. The diameter and height
of the conical tank is 6m and 5m respectively. If the tank is initially full a) Derive a
relationship between height and time. b) how long will it take for 75% of water to flow
out of the tank.
 Problem-3 (1/2)
A storage tank that is 2.0 m in diameter is being filled at the rate of 2.0 m3/min. When the height of the liquid is 2 m in
the tank, the bottom of the tank springs a leak. The rate of leaking is proportional to the head of fluid so that it is
leaking at a rate of 0.4h m3/min, where h is in m.(i) Derive a relationship between height and time. (ii) What is the
height in the tank after 60min.(iii) What is the steady state height of the fluid in the tank?

Solution:
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = −
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑 𝑉𝜌
= 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1) [ ρ is constant ]
𝑑𝑡

𝑑 𝑉
= 𝐹1 − 𝐹2
𝑑𝑡
𝑑 𝜋𝑟 2ℎ
= 2 − 0.4ℎ
𝑑𝑡
A = πr2 = π*(1)2 = π
 Problem-3 (2/2)
𝑡 ℎ
1 𝑑 ℎ
‫׬ 𝜋 = 𝑡𝑑 𝑜׬‬ℎ 2−0.4ℎ
------- (2)
𝜋 2−0.4ℎ1
(i) 𝑡 = 𝑙𝑛
0.4 2−0.4ℎ
(ii) At t = 0 ; h=2
At t= 60 min ; h= h1
Sub. in eqn.(2)
h1= 4.55 m
(i) At steady state
𝑑 𝜋𝑟 2 ℎ
= 2 − 0.4ℎ
𝑑𝑡
2-0.4h =0
h = 5m
 Problem-4 (1/2)
A water tank 6m high and 3m in diameter is drained by an orifice at the bottom. The exit velocity is given by V2=
0.61*(2gh)0.5 m/sec . The orifice is 100mm in diameter and the tank is initially full. a) Derive a relationship between height
and time. b) How long will it take to drain the tank to half its capacity.

Solution:
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑖𝑛 − 𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡
𝑀𝑎𝑠𝑠
𝑑 𝑉𝜌
= 𝐹1 𝜌 − 𝐹2 𝜌 ---------- (1) { no input and ρ is constant }
𝑑𝑡
𝑑(𝐴 × ℎ)
= − 𝐹2
𝑑𝑡
Given Velocity, V2= 0.61*(2gh)0.5 m/sec
F2 = V2* A orifice ( m3/sec) = 0.61*(2* 9.81*h)0.5 * π/4 * (100*10-3)2 m3/sec
F2 = 0.212 h0.5
A = ATank = π/4 * (3)2 = 7.065 m2
 Problem-4 (2/2)
𝑑ℎ
7.065 = −0.0212 ℎ
𝑑𝑡
3 𝑑ℎ −3 𝑡
‫׬‬6 ℎ = −3 × 10 ‫׬‬0 𝑑𝑡

𝑡 = −333.34 × 2 × 3− 6

t=478.3 Sec
 Enclosed Tank Vessel

• This case is similar to the above except that the vessel is wholly enclosed
• Pressure P0 above the surface becomes a variable instead of a constant. Movement of the surface up and down will
compress and expand the gas and cause the pressure to change.
• Assuming an ideal gas, using the equation of state
𝑃𝑜 𝑉𝐺 = 𝑛𝑅𝑇𝐺 ------(1)
• Under the assumption of adiabatic conditions, the temperature of the system compression can be computed.
• Since no heat is lost from the system and all the work is converted into sensible heat, the energy balance on the
closed system becomes
∆𝑈 + ∆𝐾𝐸 + ∆𝑃𝐸 = 𝑄 − Ẁ -------- (2)
where KE = kinetic energy, PE = potential energy
• For adiabatic conditions Q = 0 and we will also assume that Δ(KE) = 0 and Δ(PE) = 0 for this system.
• Therefore, the energy balance becomes
∆𝑈 = −∆Ẁ -------- (3)
• Applying this to a differential element in the gas phase,
𝑑𝑈 = −𝑑Ẁ ------- (4)
• The internal energy can be related to the temperature of the system
𝑑𝑈 = 𝐶𝑉 𝑑𝑇𝐺 ------ (5)
where Cv is the heat capacity at constant volume
• The only form of work in this system is PV work so that
𝑑Ẁ = 𝑃𝑜 𝑑Ṽ -------- (6) [ work for mechanically reversible non flow process is always given by dW=PdV]
• Ṽ is the specific volume of the gas
• substituting equations (5 ), (6 ) in equation( 4) gives
𝐶𝑉 𝑑𝑇𝐺 = −𝑃𝑜 𝑑Ṽ
𝑃𝑜
𝐶𝑉 𝑑𝑇𝐺 = − 𝑑𝑉𝐺 ------ (7)
𝑚

• where m = the mass of the system.

• Using the ideal gas law and assuming Cv is constant,substituting eqn(1) in equation (7 ) and integrated as
𝑛𝑅𝑇𝐺
𝐶𝑉 𝑑𝑇𝐺 = − 𝑑𝑉𝐺
𝑚𝑉𝐺
𝑇𝐺 𝑉𝐺
𝑑𝑇𝐺 𝑅 𝑑𝑉𝐺
න =− න
𝑇𝐺0 𝑇𝐺 𝑀𝐶𝑉 𝑉𝐺0 𝑉𝐺
where TG0 , TG = Temperature of gas initially and during the process
VGO, VG = Volume of gas initially and during the process.
 𝑇𝐺 𝑅 𝑉𝐺0
𝑙𝑛 = 𝑙𝑛
𝑇𝐺0 𝑀𝐶𝑉 𝑉𝐺
𝑅
𝑇𝐺 𝑉𝐺0 𝑀𝐶𝑉
=
𝑇𝐺0 𝑉𝐺
• The volume of the gas can be computed at any time from
𝑉𝐺 = 𝑉0 − 𝐴𝑍
where V0 = total tank volume, A = cross-sectional area of the tank
• Other Equations
𝑑𝑍
𝐴 = 𝐹1 − 𝐹2
𝑑𝑡
𝐹1 = 𝐶𝑉1 𝑃1 − 𝑃2
𝐹2 = 𝐶𝑉2 𝑃2 − 𝑃3
𝑃2 = 𝑃𝑂 + 𝜌𝑔𝑍
Information flow diagram
 Enclosed Tank With Reaction

K1
𝐴+𝐵 ⇄𝐶+𝐷
K2
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝑅𝑎𝑡𝑒 𝐼𝑛 𝑅𝑎𝑡𝑒 𝑜𝑢𝑡
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = − + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
• Component A balance

𝑑 𝑉𝐶𝐴2
= 𝐹1 𝐶𝐴2 − 𝐹2 𝐶𝐴2 − 𝑉𝐾1 𝐶𝐴2 𝐶𝐵2 + 𝑉𝐾2 𝐶𝐶2 𝐶𝐷2
𝑑𝑡

• Component B balance

𝑑 𝑉𝐶𝐵2
= 𝐹1 𝐶𝐵2 − 𝐹2 𝐶𝐵2 − 𝑉𝐾1 𝐶𝐴2 𝐶𝐵2 + 𝑉𝐾2 𝐶𝐶2 𝐶𝐷2
𝑑𝑡

• Component C balance

𝑑 𝑉𝐶𝐶2
= −𝐹2 𝐶𝐶2 + 𝑉𝐾1 𝐶𝐴2 𝐶𝐵2 − 𝑉𝐾2 𝐶𝐶2 𝐶𝐷2
𝑑𝑡

• Component D balance

𝑑 𝑉𝐶𝐷2
= −𝐹2 𝐶𝐷2 + 𝑉𝐾1 𝐶𝐴2 𝐶𝐵2 − 𝑉𝐾2 𝐶𝐶2𝐶𝐷2
𝑑𝑡
𝑇𝑎𝑘𝑒 𝑅 = 𝑉𝐾1 𝐶𝐴2 𝐶𝐵2 − 𝑉𝐾2 𝐶𝐶2 𝐶𝐷2

𝑑 𝑉𝐶𝐴2
= 𝐹1 𝐶𝐴2 − 𝐹2 𝐶𝐴2 − 𝑅
𝑑𝑡

𝑑 𝑉𝐶𝐵2
= 𝐹1 𝐶𝐵2 − 𝐹2 𝐶𝐵2 − 𝑅
𝑑𝑡

𝑑 𝑉𝐶𝐶2
= 𝑅 − 𝐹2 𝐶𝐶2
𝑑𝑡

𝑑 𝑉𝐶𝐷2
= 𝑅 − 𝐹2 𝐶𝐷2
𝑑𝑡
IFD Enclosed Reaction
6
 Chlorination Of Benzene
• The chlorination of benzene produces monochlorobenzene, dichlorobenzene, and trichlorobenzene through the
successive reactions
𝐾1
𝐶6 𝐻6 + 𝐶𝑙2 𝐶6 𝐻5 𝐶𝑙 + 𝐻𝐶𝑙
Benzene(B) Chlorine(C)
MonoChlorobenzene(M)

𝐾2
𝐶6 𝐻5 𝐶𝑙 + 𝐶𝑙2 𝐶6 𝐻4 𝐶𝑙2 + 𝐻𝐶𝑙

Dichlorobenzene(D)

𝐾3
𝐶6 𝐻4 𝐶𝑙2 + 𝐶𝑙2 𝐶6 𝐻3 𝐶𝑙3 + 𝐻𝐶𝑙

Trichlorobenzene(T)
• Reactions are carried out in a lead-lined or iron vessel,
as shown in Figure .
• Ferric chloride (FeCl3) is used as a catalyst.
• The vessel is fitted with cooling coils, since the
reactions are exothermic.
• There is a reflux condenser, which returns vaporized
chlorobenzenes to the system, while allowing the
hydrogen chloride (HCl) and excess chlorine vapour to
leave the system.
• To maintain the reacting mixture at a uniform
temperature and to minimize mass transfer effects, the
reacting mixture is well agitated. The amount of the
chlorine gas which dissolves in the liquid phase is
limited by the solubility of chlorine in the reacting
mixture.
The following assumptions can be made:
• There is no liquid or vapour hold-up in the reflux condenser, i.e., no dynamics are involved.
• The system operates under isothermal and isobaric conditions.
• Volume changes in the reacting mixture are negligible.
• Hydrogen chloride has a negligible solubility in the liquid mixture. Hydrogen chloride vaporizes and leaves the
system.
• There is negligible mass transfer resistance between the gaseous Cl2 and the Cl2 in solution, i.e., the Cl2 goes
immediately into solution up to the solubility limit.

where, ND = moles of Di-chlorobenzene

NB = moles of benzene NT = moles of Tri-chlorobenzene
NC = moles of chlorine V = volume of reactor
NM = moles of Mono-chlorobenzene
Component Balance for all components
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝑅𝑎𝑡𝑒 𝐼𝑛 𝑅𝑎𝑡𝑒 𝑜𝑢𝑡
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = − + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
• The material balance for benzene is
1 𝑑𝑁𝐵 𝐾1 𝑁𝐵 𝑁𝐶
=−
𝑉 𝑑𝑡 𝑉 𝑉
• Since Concentration = No. of Moles/ Volume of solution i.e. C = N/ V
𝑑𝑁𝐵 𝐾1 𝑁𝐵 𝑁𝐶
=−
𝑑𝑡 𝑉
• The material balance for mono-chlorobenzene is
𝑑𝑁𝑀 𝐾1 𝑁𝐵 𝑁𝐶 𝐾2 𝑁𝑀 𝑁𝐶
= −
𝑑𝑡 𝑉 𝑉
• The material balance for di-chlorobenzene is
𝑑𝑁𝐷 𝐾2 𝑁𝑀 𝑁𝐶 𝐾3𝑁𝐷 𝑁𝐶
= −
𝑑𝑡 𝑉 𝑉
• The material balance for tri-chlorobenzene is
𝑑𝑁𝑇 𝐾3 𝑁𝐷 𝑁𝐶
=
𝑑𝑡 𝑉
• The material balance for chlorine is
𝑑𝑁𝑐 𝐾1 𝑁𝐵 𝑁𝐶 𝐾2 𝑁𝑀 𝑁𝐶 𝐾3 𝑁𝐷 𝑁𝐶
=𝐹− − −
𝑑𝑡 𝑉 𝑉 𝑉

Order of Magnitude Analysis for Chlorination of Benzene

𝑁𝐵 𝑁𝐶 𝑁𝑀 𝑁𝐷 𝑁𝑇 𝑉 𝑡
𝑁𝐵 ∗ = 𝑁𝐶 ∗ = 𝑁𝑀 ∗ = 𝑁𝐷 ∗ = 𝑁𝑇 ∗ = 𝜏= 𝑡∗ =
𝑁𝐵𝑂 𝑁𝐵𝑂 𝑁𝐵𝑂 𝑁𝐵𝑂 𝑁𝐵𝑂 𝐾1 𝑁𝐵𝑂 𝜏
Introducing these dimensionless variables, the describing differential equations becomes
𝑑𝑁𝐵 𝐾1 𝑁𝐵 𝑁𝐶
=−
𝑑𝑡 𝑉
𝑁𝐵𝑜 𝑑𝑁𝐵 ∗ 𝐾1 𝑁𝐵 ∗ 𝑁𝐵𝑂 𝑁𝐶 ∗ 𝑁𝐵𝑂
=−
𝜏 𝑑𝑡 ∗ 𝑉
𝑑𝑁𝐵 ∗
= −𝑁𝐵 ∗ 𝑁𝐶 ∗ ---------- (1)
𝑑𝑡 ∗

𝑑𝑁𝑀 ∗ 𝐾2
= 𝑁𝐵 ∗ 𝑁𝐶 ∗ − 𝑁𝑀 ∗ 𝑁𝐶 ∗ ------------------ (2)
𝑑𝑡 ∗ 𝐾1

𝑑𝑁𝐷 ∗ 𝐾2 𝐾3
= 𝑁𝑀 ∗ 𝑁𝐶 ∗ − 𝑁𝐷 ∗ 𝑁𝐶 ∗ ---------------- (3)
𝑑𝑡 ∗ 𝐾1 𝐾1

𝑑𝑁𝑇 ∗ 𝐾3
= 𝑁𝐷 ∗ 𝑁𝐶 ∗ ------------- (4)
𝑑𝑡 ∗ 𝐾1

𝑑𝑁𝐷 ∗ 𝐹𝑉𝜏 𝐾2 𝐾3
= − 𝑁𝐵 ∗ 𝑁𝐶 ∗ − 𝑁𝑀 ∗ 𝑁𝐶 ∗ − 𝑁𝐷 ∗ 𝑁𝐶 ∗ ----------- (5)
𝑑𝑡 ∗ 𝑁𝐵𝑂 𝐾1 𝐾1
Given
• K I = 510 (kg mol/m3) -1 (hr) -1
• K2 = 64 (kg mol/m3) -1 (hr) -1
• K3= 2.1 (kg mol/m3) -1 (hr) -1
volume of liquid in the reactor remains constant at 1.46 m3/kg mol of initial benzene charge.
• Equation (1) stays the same, as
𝑑𝑁𝐵 ∗
∗ = −𝑁𝐵 ∗ 𝑁𝐶 ∗ --------- (6)
𝑑𝑡
𝑑𝑁𝑀 ∗
∗ = 𝑁𝐵 ∗ 𝑁𝐶 ∗ − 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗ -------- (7)
𝑑𝑡
𝑑𝑁𝐷 ∗
∗ = 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗ − 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗ ---------- (8)
𝑑𝑡
𝑑𝑁𝑇 ∗
∗ = 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗ ----------- (9)
𝑑𝑡
 order of Magnitude analysis

10-4 10-3 10-2 10-1 100 101 102 103 104

 𝑑𝑁𝐵 ∗
= −𝑁𝐵 ∗ 𝑁𝐶 ∗ --------- (6)
𝑑𝑡 ∗

• This implies that all terms in the benzene disappearance equation are of equal importance
𝑑𝑁𝑀 ∗
∗
= 𝑁𝐵 ∗ 𝑁𝐶 ∗ − 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗
𝑑𝑡
• This implies that the disappearance term due to the mono-chlorobenzene is approximately one order-of-magnitude
less important than the generation term due to differential equation. Equation (4.1.9) becomes or benzene. Both
terms should be∗retained in the
𝑑𝑁𝐷
∗
= 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗ − 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡
OR
∗
𝑑𝑁𝐷
7.068 ∗
= 𝑁𝑀 ∗ 𝑁𝐶 ∗ − 0.0328𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡
• Comparing equation (4.1.16) to (4.1.13) or (4.1.14) shows that the dichlorobenzene response is approximately one
order-of-magnitude slower than that for the benzene consumption or mono-chlorobenzene generation response.
Equation (4.1.10) becomes
𝑑𝑁𝑇 ∗
∗
= 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡
OR
∗
𝑑𝑁𝑇
243 ∗
= 𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡
• This implies that the trichlorobenzene response is approximately two orders-of-magnitude slower than that for
monochlorobenzene.
Information flow diagram - Chlorination of Benzene
 Autocatalytic Reaction
• Selected for mathematical analysis is the catalytic thermal decomposition of a single compound A into two products
B and C, of which B is the autocatalytic agent. Thus, A can decompose via two routes, a slow uncatalysed one (kl)
and another catalysed by B(k3). The three essential kinetic steps are

 These equations show that the autocatalytic agent B forms a complex, AB, with rate k2. Next, the complex AB
decomposes with rate k3, thereby releasing B in addition to forming B and C. Reactions k2 and k3 together form the
path by which most of A decomposes. Reaction k1 is the starter, but continues concurrently with k2 and k3 as long
as there is any A. The rates of formation of A, B, C, and AB, in accordance with the kinetic steps, are
 CA, CB, and CAB are molar concentrations of A, B, AB
• The basic material balances can be derived for scaled variables. The dimensionless variables are
𝐶 𝐶𝐴 𝑡
𝐶∗ = , 𝑆𝑖𝑚𝑖𝑙𝑎𝑟𝑙𝑦 𝐶𝐴 ∗ = 𝑎𝑛𝑑 𝑠𝑜 𝑜𝑛. 𝐴𝑙𝑠𝑜 𝑡 ∗ =
𝐶𝐴𝑂 𝐶𝐴𝑂 1/𝐾1
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝑅𝑎𝑡𝑒 𝐼𝑛 𝑅𝑎𝑡𝑒 𝑜𝑢𝑡
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = − + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
• and the material balance equations for A, B, C, AB
𝑑𝐶𝐴
= −𝐾1 𝐶𝐴 − 𝐾2 𝐶𝐴 𝐶𝐵
𝑑𝑡
𝑑𝐶𝐵
= 𝐾1 𝐶𝐴 − 𝐾2 𝐶𝐴 𝐶𝐵 + 2𝐾3 𝐶𝐴𝐵
𝑑𝑡
𝑑𝐶𝐶
= 𝐾1 𝐶𝐴 + 𝐾3𝐶𝐴𝐵
𝑑𝑡
𝑑𝐶𝐴𝐵
= 𝐾2 𝐶𝐴 𝐶𝐵 − 𝐾3𝐶𝐴𝐵
𝑑𝑡
• Using dimensionless form
𝑑𝐶𝐴 ∗
𝐾1 𝐶𝐴𝑂 ∗
= −𝐾1 𝐶𝐴 ∗ 𝐶𝐴𝑂 − 𝐾2 𝐶𝐴 ∗ 𝐶𝐴𝑂 𝐶𝐵 ∗ 𝐶𝐵𝑂
𝑑𝑡
𝑑𝐶𝐴 ∗ ∗ 𝐾2 ∗ ∗
= −𝐶 𝐴 − 𝐶𝐴𝑂 𝐶𝐴 𝐶𝐵
𝑑𝑡 ∗ 𝐾1
∗
𝑑𝐶𝐴 ∗ ∗ ∗
= −𝐶 𝐴 − 𝛽𝐶 𝐴 𝐶𝐵
𝑑𝑡 ∗
𝑑𝐶𝐵 ∗ ∗ 𝐾2 ∗ ∗ 𝐾3 ∗
= 𝐶 𝐴 − 𝐶 𝐴𝑂 𝐶𝐴 𝐶𝐵 + 2 𝐶𝐴𝐵
𝑑𝑡 ∗ 𝐾1 𝐾1
∗
𝑑𝐶𝐵 ∗ ∗ ∗ ∗
= 𝐶 𝐴 − 𝛽𝐶 𝐴 𝐶 𝐵 + 2𝛼𝐶 𝐴𝐵
𝑑𝑡 ∗
Note: A+2B  C+D ------ If K is the rate of disappearance of A, the rate of disappearance of B will be 2K because 2
moles of B reacts with each mole of A.
𝑑𝐶𝐶 ∗ ∗ 𝐾3
∗
= 𝐶 𝐴 + 𝐶𝐴𝐵 ∗
𝑑𝑡 𝐾1
∗
𝑑𝐶𝐶 ∗ ∗
= 𝐶 𝐴 + 𝛼𝐶 𝐴𝐵
𝑑𝑡 ∗
 𝑑𝐶𝐴𝐵 ∗ 𝐾2 ∗ ∗ 𝐾3
∗
= 𝐶 𝐴𝑂 𝐶𝐴 𝐵 𝐶 − 𝐶𝐴𝐵 ∗
𝑑𝑡 𝐾1 𝐾1
∗
𝑑𝐶𝐴𝐵
∗
= 𝛽𝐶𝐴 ∗ 𝐶𝐵 ∗ − 𝛼𝐶𝐴𝐵 ∗
𝑑𝑡
𝐾3
𝛼=
𝐾1
𝐾2
𝛽= 𝐶
𝐾1 𝐴𝑂
For β = 104, it has been observed that α, called the degree of autocatalysis, can be categorized as
• α = 1to 10, the reaction is barely noticeably autocatalytic
• α= 11 to 100, the reaction is mildly autocatalytic
• α = 101 to 1000, the reaction is strongly autocatalytic
Information Flow Diagram
 Temperature Effects In Stirred Tank Reactors
• CSTR , which is used for the decomposition of hydrogen
peroxide.
• The reaction is first-order and homogeneously catalyzed.
• The reactant, hydrogen peroxide (H202), and the catalyst,
sodium hydroxide, are fed into the reactor, while the product,
water, and unreacted peroxide are continuously removed.
• The exothermic heat of reaction is continuously removed
through a cooling water jacket which surrounds the reactor.
𝑁𝑎𝑂𝐻
𝐻2 𝑂2 𝐻2 𝑂

Notations used  U - heat-transfer coefficient  To- inlet feed temperature  QC- coolant flowrate (mass/time)
 H- heat of reaction (cal/mol)  A - heat-transfer area  T- outlet temperature  V- volume of the reactor
 k - reaction rate constant  TA - average coolant temperature  Co- inlet peroxide concentration
 C - concentration of H2O2  F0 - flow rate out of the reactor (mol/vol)
(mol/vol)  ρ – Density of fluid
• H2O2 balance
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝑅𝑎𝑡𝑒 𝐼𝑛 𝑅𝑎𝑡𝑒 𝑜𝑢𝑡
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = − − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
𝑜𝑓 𝐻2 𝑂2 𝑜𝑓 𝐻2 𝑂2
𝐻2 𝑂2 𝑜𝑓 𝐻2 𝑂2
𝑑𝐶
𝑉 = −𝑉𝑘𝐶 − 𝐹0 𝐶 − 𝐶0
𝑑𝑡
• Energy balance
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 = 𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑜 − 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡 𝑜𝑓 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑜𝑓 𝐸𝑛𝑒𝑟𝑔𝑦
𝑑𝑇
𝜌𝑉𝐶𝑝 = 𝐻𝑉𝑘𝐶 − 𝑈𝐴 𝑇 − 𝑇𝐴 − 𝜌 𝐹0𝐶𝑝 𝑇 − 𝑇0
𝑑𝑡
• Assumptions
• The heat removal driving force term involving (T- TA) is modelled by assuming that the cooling water temperature in the
jacket is an arithmetic average of the input and output cooling temperatures. Employing this assumption, a steady-state
energy balance across the cooling water jacket gives
• Wall resistance is neglected and is taken as T
• Steady state Energy balance around the jacket
I/P – O/P + Heat added = 0
𝑄𝐶 𝐶𝑃 𝑇𝐴 − 𝑇𝑖𝑛 − 𝑄𝐶 𝐶𝑃 𝑇 − 𝑇𝐴 + 𝑈𝐴 𝑇 − 𝑇𝐴 = 0
𝑇𝑖𝑛 + 𝑇𝐴
𝑇𝐴 =
2
• Substituting and rearranging yields
𝑇 − 𝑇𝑖𝑛
𝑇 − 𝑇𝐴 =
𝑈𝐴
2 1−
𝑄𝐶 𝐶𝑝
• For laminar flow in the coolant jacket, the overall heat-transfer coefficient is
related to the coolant mass flow rate according to
U= C1 Qc1/3 where C1 = constant
• The reaction rate constant follows the Arrhenius temperature dependency of
𝐸
𝑘 = 𝑘0 𝑒 −𝑅𝑇
where k0 - frequency factor, a constant and E - activation energy
Information Flow diagram
 Boiling in an open vessel
• The vapour pressure exerted by liquid varies with temperature
• Vaporization can be considered negligible until the temperature has reached the
boiling point.
• For sensible heat change, energy balance is given by
Rate of 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
Accumulation of
= 𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑜 − 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡 𝑜𝑓
Energy or change
𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
of sensible heat
𝑑 𝑉𝜌𝐶𝑃𝐿 𝑇
=𝑄−0
𝑑𝑡
• The phenomenon of the boiling of a pure fluid provides a situation in which the
vapor pressure(PV ) of the fluid tends to exceed the total pressure(P) of the system.
• This gives rise to a stream of vapor rising from the liquid
• Because there is no resistance to departure of this vapour, a sufficient flow is
emitted that prevents the temperature from raising beyond boiling pt.
• The minute difference between the Pv and P (i.e Pv > P ) is sufficient to provide the
vapour flow.
 Boiling in an open vessel
• During boiling , energy balance is given by
Rate of 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓
Accumulation of 𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑜
= − 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡 𝑜𝑓
Energy or change
𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
of sensible heat
𝑑 𝑉𝜌𝐶𝑃𝐿 𝑇 𝐾𝑔
= 𝑄 − 𝑣λ 𝑣 = 𝑣𝑎𝑝𝑜𝑟 𝑏𝑜𝑖𝑙𝑜𝑓𝑓 𝑟𝑎𝑡𝑒
𝑑𝑡 𝑠𝑒𝑐
𝑑 𝑉𝜌𝐶𝑃𝐿 𝑇
≪< 𝑄
𝑑𝑡
Therefore 𝑄 = 𝑣λ
• The phenomena of boiling is such that these are virtually non-interacting
i.e the temperature responds to only pressure P and vapour flow responds only
to heat flux.
 Boiler or boiling in a jacketed vessel
• Most industrial boilers are enclosed vessels, as shown in Figure below. In order to model this system,
the following material and energy balances are used.
Q= rate of heat supplied to boiler
F1= volumetric flow rate of liquid into boiler
λ= heat of vaporization at the system temperature
T1 , T and Tr = Inlet , system and reference temperature
CpL= liquid heat capacity
ρ = density of the liquid
v = Rate of vapour boil up rate (Kg/s)
Ve = Rate of Vapor removed
VG, VL = Volume of Vapor and Liquid
 Boiler or boiling in a jacketed vessel
Energy Balance (Liquid Phase)
Rate of Rate of Rate of Rate of Rate of
Accumulation of = Energy into − Energy out of + Generation − dissipation
Total Energy the system the system of Energy of energy

𝟎 = 𝛒𝐅𝟏 𝐂𝐩𝐋 T1 − Tr + 𝐐 − 𝐯 λ + CpL T − Tr

𝐝 𝐕𝐋 𝐂𝐏𝐋 𝛒 𝐓 − 𝐓𝐫
𝑨𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒊𝒐𝒏 =
𝐝𝐭
𝐝 𝐕𝐋 𝐂𝐏𝐋 𝛒 𝐓− 𝐓𝐫
Note: 𝑸 ≫≫ hence accumulation is neglected.
𝐝𝐭

Mass Balance (Liquid Phase):

𝐝 𝛒𝐕𝐋
= 𝛒𝐅𝟏 – 𝐯
𝐝𝐭
 Boiler or boiling in a jacketed vessel
Energy Balance (Vapor Phase; assume equilibrium)

Note: Assuming equilibrium to exist at all times between liquid and vapour. Therefore energy balance for the
vapour side is not necessary and the vapour temp. is taken same as Liquid temp.
𝐓𝐆 = 𝐓𝐋 = 𝐓
Mass Balance (Vapor Phase)
𝐝𝐦
= 𝐯 − 𝐯𝐞
𝐝𝐭
where 𝑣 = mass in vapor phase
𝑣𝑒 = mass flow of vapor through exit valve
Equation of State (Vapor Phase):
𝐦𝐑𝐓
𝐏𝐕𝐆 =
𝐌𝐖
 Boiler or boiling in a jacketed vessel
Size Relation:

V = VL + VG

where V = volume of the system.

Valve Equation

A steady-state mechanical energy balance around the valve results in the following
algebraic relation for flow of a gas across a valve .
ve = K v P P − Po

Where Kv
Boiler or boiling in a jacketed vessel -IFD

For any boiling phenomena, use this equation

For any boiling phenomena, use this equation

 VAPOR LIQUID EQUILIBRIUM(VLE)
• Simple Rules of Vapor Liquid Equilibrium
a. Vapor pressure of liquid depends on temperature.
b. Heat input raises vapor pressure of liquid.
c. A liquid boils when its vapor pressure equals the system pressure.
d. Higher the vapor pressure lowers the boiling point.
e. Volatile liquids have high vapor pressure.
f. The vapor pressure and hence the boiling point of a liquid mixture depends on the relative
amounts of the components in the mixture
g. At equilibrium, the temperature and pressure of the liquid and vapor phases will be equal, but
the compositions will not
 VAPOR LIQUID EQUILIBRIUM(VLE)
 In the Figure , the vessel contains 3 miscible fluids of components A, B, C.
xa, xb, xc are mole fractions of components A, B and C resp. in Liquid phase
 When the liquid boils at temperature T, the vapour stream will evolve having
composition ya, yb, yc .
 This vapour composition is generally different than the liquid composition
providing a convenient way of separating miscible components.
 When vapour composition is same as liquid composition, the system is termed
as constant boiling azeotropic mixture.
 Since vapour is issuing from liquid, it is essentially in equilibrium with liquid.
Hence chemical potential are equal.
 This can be expressed as 𝛷𝑖 𝑦𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑆𝑎𝑡 --------- (1)
Where
𝛷𝑖 = 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
𝛾𝑖 = 𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
𝑢𝑠𝑒𝑑 𝑡𝑜 𝑎𝑐𝑐𝑜𝑢𝑛𝑡 𝑓𝑜𝑟 𝑑𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑖𝑑𝑒𝑎𝑙 𝑏𝑒ℎ𝑎𝑣𝑖𝑜𝑟 𝑜𝑓
𝑚𝑖𝑥𝑡𝑢𝑟𝑒𝑠 𝑜𝑓 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒𝑠
𝑆𝑎𝑡
𝑃𝑖 = 𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒
P= total pressure
Note: VLE is used in Distillation, Absorption, Stripping
 Multi-component Bubble and Dew point
These calculation requires iterative scheme because of complex functionality i.e.
𝛷𝑖 = 𝛷 𝑇, 𝑃, 𝑦1 , 𝑦2, 𝑦3 , 𝑦4 . . . .
𝜸𝒊 = 𝜸 𝑻, 𝒙𝟏 , 𝒙𝟐, 𝒙𝟑 , 𝒙𝟒 . . . .
𝑷𝒊 𝑺𝒂𝒕 = 𝒇 𝑻

It is an iterative procedure for efficient solution of yi and xi

From eqn.(1), We can calculate Bubble point Temperature

𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑆𝑎𝑡
𝑦𝑖 =
𝛷𝑖 𝑃
𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑆𝑎𝑡
σ 𝑦𝑖 = σ =1 ----(2)
𝛷𝑖 𝑃
 Multi-component Dew point

Dew Point Temperature is calculated

𝛷𝑖 𝑦𝑖 𝑃
𝑥𝑖 =
𝛾𝑖 𝑃𝑖 𝑆𝑎𝑡

𝛷𝑖 𝑦𝑖 𝑃
σ 𝑥𝑖 = σ = 1 --------- (3)
𝛾𝑖 𝑃𝑖 𝑆𝑎𝑡
General Method for VLE calculation
Method 1:

𝑬𝒓𝒓𝒐𝒓 = 𝟏 − σ 𝒚𝒊
𝑇𝑚𝑒𝑤 = 𝑇𝑜𝑙𝑑 − 𝐺 𝑬𝒓𝒓𝒐𝒓

G= Gain factor which can vary from 101 to 102 or 0.01 to 0.001

Disadvantage - It is a custom based gain factor which varies from system to system.

Method 2: Newton-Raphson Method

Bubble Point Temperature

𝑌𝐸𝑅 = 1 − ෍ 𝑦𝑖 = 𝐸𝑟𝑟𝑜𝑟

YER = Error in Y
𝐶2𝑖
𝑆𝑎𝑡 𝐶1𝑖 +
𝑃𝑖 𝑇 =𝑒 𝐶3𝑖 +𝑇

𝐶2𝑖
𝐶1𝑖 +
𝑒 𝐶3𝑖 +𝑇
𝑦𝑖 = 𝑥1 𝛾𝑖
𝑃

C1 , C2 , C3 ----- constants for ith component

Assumption : γi is constant with temperature

N-R method
𝒇 𝑻
𝑻𝒏𝒆𝒘 = 𝑻𝒐𝒍𝒅 − ′
𝒇 𝑻

Note: Since yi is function of T ( When Σyi = 1  T i.e The temperature at which summation of y equals 1 gives the
system temperature)

𝒇 𝑻 = 𝒀𝑬𝑹 = 𝟏 − σ 𝒚𝒊 -------------- (4)

𝒅 𝟏− σ 𝒚𝒊
𝒇′ 𝑻 = [ Σ means for N component and during differentiation Σ is kept outside ]
𝒅𝑻
𝒅 𝒚𝒊
𝒇′ 𝑻 = 𝜮 --------- (5)
𝒅𝑻

Sub. from eqn.(2) into eqn.(5) and differentiating take Φi=1

𝑪
𝑺𝒂𝒕 𝑪𝟏𝒊+ 𝟐𝒊
𝜸𝒊 𝒙𝒊 𝑷𝒊 𝜸𝒊 𝒙𝒊 𝒆 𝑪𝟑𝒊+𝑻
𝒅 𝒅
𝜮 𝑷 =𝜮 𝑷
𝒅𝑻 𝒅𝑻
 𝒅𝒚𝒊 𝑪𝟐𝒊
𝜮 = 𝜮 −𝒚𝒊 𝟐
𝒅𝑻 𝑻 + 𝑪𝟑𝒊
𝒅𝒚𝒊 𝑪𝟐𝒊
𝑺𝑫𝒀 = 𝜮 = 𝜮 −𝒚𝒊 𝟐
𝒅𝑻 𝑻 + 𝑪𝟑𝒊

SDY = Summation of Differentiation of Y

𝒇 𝑻 𝒀𝑬𝑹
𝑻= 𝑻−
𝒇′ 𝑻
or 𝑻 = 𝑻 − 𝑺𝑫𝒀

Dew Point Temperature

𝑿𝑬𝑹 = 𝒇 𝑻 = 𝟏 − 𝜮𝒙𝒊 ------- ( 6)
XER = Error in x
𝒅 𝟏− σ 𝒙𝒊
𝒇′ 𝑻 = [ Σ means for N component and during differentiation Σ is kept outside ]
𝒅𝑻
𝒅 𝒙𝒊
𝒇′ 𝑻 = 𝜮 --------- (7)
𝒅𝑻
Sub. from eqn.(3) into eqn.(6) and differentiating take Φi=1
𝑦𝑖 𝑃
𝑦𝑖 𝑃 𝑑 𝐶2𝑖
𝑑 𝐶 +
𝛾𝑖 𝑃𝑖 𝑆𝑎𝑡 𝛾𝑖 𝑒
1𝑖 𝐶 +𝑇
3𝑖
𝛴 =𝛴
𝑑𝑇 𝑑𝑇
𝐶2𝑖
𝑆𝐷𝑋 = 𝛴 𝑥𝑖 2
𝑇 + 𝐶3𝑖

SDX = Summation of Differentiation of X

𝑋𝐸𝑅
𝑇= 𝑇−
𝑆𝐷𝑋
 Generalized Phase Transformation
Classification of Enthalpy changing unit operations
I/P stream Heat added O/P stream Unit O/P

Liquid + ve Liquid only HEATER

Liquid - ve Liquid only COOLER

Vapor +ve Vapor only SUPERHEATER

Vapor -ve Vapor only DE-SUPERHEATER

Liquid None Vap + Liq FLASH (ADIABATIC)

Liquid +ve Vapor only BOILER, VAPORIZER

Vapor -ve Vap+ Liq CONDENSOR (PARTIAL)

Note: Common approximation for
Vapor -ve Liquid only CONDENSOR (TOTAL) those operation resulting in
simultaneous vapour and liquid
FLASHING H.E ,DISTILLATION streams is to assume that both the
Liquid +ve Vap +Liq streams are in equilibrium with each
COLUMN(REBOILER) other.
 Flash Vaporization OR Condensation
Steady state Overall Mass balance
Mass I/P = Mass O/P

F = V +L --------- (1)

Steady state Heat Balance

Energy I/P = Energy O/P

𝐅𝒉𝑭 + 𝐐 = 𝐕𝑯𝑽 + 𝐋𝒉𝑳 -------- (2)

Let R = V/ F = Vapor feed split

Divide eqn.(2) by F
𝑸 𝑽 𝑳
𝒉𝑭 + = 𝑯𝑽 + 𝒉𝑳
𝑭 𝑭 𝑭
Using R and L= F - V

𝑸 (𝑭 − 𝐕)
𝒉𝑭 + = 𝐑𝑯𝑽 + 𝒉𝑳
𝑭 𝑭
 𝑸
𝒉𝑭 +𝑭 −𝒉𝑳
𝐑= ------- (3)
𝑯𝑽 − 𝒉𝑳

Steady state component balance

𝐅 𝒁𝑭𝒊 = 𝐕𝒚𝒊 + 𝐋𝒙𝒊 -------- (4)

𝒚𝒊 𝑷𝒊 𝑺𝒂𝒕
𝐄𝐪𝐮𝐢𝐥𝐢𝐛𝐫𝐢𝐮𝐦 𝐑𝐚𝐭𝐢𝐨 = 𝑲𝒊 = = 𝜸𝒊 -------- (5)
𝒙𝒊 𝑷

Note: The most commonly used ways of exploiting VLE in column calculation is equilibrium constant or K value and relative
volatility.

 K value provides a linear relation for each composition between its concentration in Vapor and liquiud

i.e y= K x

𝒚𝒊 𝑷𝒊 𝑺𝒂𝒕
Thus 𝑲𝒊 = = 𝜸𝒊
𝒙𝒊 𝑷

Dividing eqn.(4) by xi and using eqn.(1)

𝐅 𝒁𝑭𝒊 𝐕𝒚𝒊
= +𝐋 ------- (6)
𝒙𝒊 𝒙𝒊
Dividing eqn.(6) by F
𝒁𝑭𝒊 𝑲𝒊 𝑭−𝑽
𝒚𝒊 = 𝑽 +
𝑭 𝑭
𝑲𝒊

Rearranging the above equation

𝑲𝒊
𝒚𝒊 = 𝒁𝑭𝒊 ------------- Rachford-Rice Equation
𝟏+𝑹 𝑲𝒊 −𝟏

𝒀𝑬𝑹 = 𝟏 − ෍ 𝒚𝒊

𝒅𝒚𝒊 𝑪𝟐𝒊
෍ = ෍ −𝒚𝒊 𝟐
𝒅𝑻 𝑻 + 𝑪𝟑𝒊

𝒀𝑬𝑹
𝐓= 𝑻−
𝐝𝒚
σ 𝒊
𝒅𝑻
 𝑇 𝑏𝑇 2
𝐶𝑃 = 𝑎 + 𝑏𝑇 𝐻= ‫׬‬0 𝐶𝑝 𝑑𝑡 = 𝑎𝑇 + 2 +𝐶

For liquids : C = 0
For Vapor : C=λ (latent heat of vaporization)
In the Text book, notations are;
HV = AVi T + BVi T 2 + λ
hL = ALi T + BLi T 2
Where AVi and ALi = a
BVi and BLi = b/2
Flash Vaporization OR Condensation-IFD
 Partial Condenser
 If the condensate temperature is specified, then the vapour temperature leaving the condenser is also specified

 Instead of calculating the temperature by Newton-Raphson method we calculate R by NR method since equilibrium temp. is
specified.

When partial condenser we differentiate with respect to R.

𝑲𝒊
𝒚𝒊 = 𝒁𝑭𝒊
𝟏 + 𝑹 𝑲𝒊 − 𝟏

𝒅𝒚𝒊 𝑲𝒊 − 𝟏
= −𝒚𝒊
𝒅𝑹 𝟏 + 𝑹 𝑲𝒊 − 𝟏
And

𝟏 − σ 𝒚𝒊
𝑹=𝑹+
𝒅𝒚
σ 𝒊
𝒅𝑹