CHLORINATION OF BENZENE

The chlorination of benzene produces monochlorobenzene, dichlorobenzene, and

trichlorobenzene through the successive reactions
K1
C6H6 + Cl2 C6H5Cl + HCl
Benzene(B) Chlorine(C) MonoChlorobenzene(M)
K2
C6H5CI + Cl2 C6H4Cl2 + HCl
Dichlorobenzene(D)
K3
C6H4Cl2 + Cl2 C6H3Cl3 + 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:
1. There is no liquid or vapour hold-up in the reflux condenser, i.e., no dynamics are involved.
2. The system operates under isothermal and isobaric conditions.
3. Volume changes in the reacting mixture are negligible.
4. Hydrogen chloride has a negligible solubility in the liquid mixture. Hydrogen chloride
vaporizes and leaves the system.
5. 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.
NB = moles of benzene
Nc = moles of chlorine
NM = moles of Mono-chlorobenzene
ND = moles of Di-chlorobenzene
NT = moles of Tri-chlorobenzene
V = volume of reactor

Component Balance for all component

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 𝐾3 𝑁𝐷 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
𝑁𝐵 ∗ = 𝑁𝐶 ∗ = 𝑁𝑀 ∗ = 𝑁𝐷 ∗ = 𝑁𝑇 ∗ = 𝝉=
𝑵𝑩𝑶 𝑵𝑩𝑶 𝑵𝑩𝑶 𝑵𝑩𝑶 𝑵𝑩𝑶 𝑲𝟏 𝑵𝑩𝑶

𝑡
𝒕∗ =
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 ∗
𝑑𝑡 ∗
𝑑𝑁𝑀 ∗ ∗ ∗ 𝐾2
∗
= 𝑁𝐵 𝑁𝐶 − 𝑁𝑀 ∗ 𝑁𝐶 ∗
𝑑𝑡 𝐾1
𝑑𝑁𝐷 ∗ 𝐾2 ∗ ∗ 𝐾3 ∗ ∗
= 𝑁𝑀 𝑁𝐶 − 𝑁 𝑁
𝑑𝑡 ∗ 𝐾1 𝐾1 𝐷 𝐶
𝑑𝑁𝑇 ∗ 𝐾3 ∗ ∗
= 𝑁 𝑁
𝑑𝑡 ∗ 𝐾1 𝐷 𝐶
𝑑𝑁𝐷 ∗ 𝐹𝑉𝜏 ∗ ∗ 𝐾2 ∗ ∗ 𝐾3 ∗ ∗
= − 𝑁𝐵 𝑁𝐶 − 𝑁𝑀 𝑁𝐶 − 𝑁 𝑁
𝑑𝑡 ∗ 𝑁𝐵𝑂 𝐾1 𝐾1 𝐷 𝐶

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 (4.1.7) stays the same, as
𝑑𝑁𝐵 ∗
= −𝑁𝐵 ∗ 𝑁𝐶 ∗
𝑑𝑡 ∗
𝑑𝑁𝑀 ∗
= 𝑁𝐵 ∗ 𝑁𝐶 ∗ − 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗
𝑑𝑡 ∗
𝑑𝑁𝐷 ∗
= 0.1255𝑁𝑀 ∗ 𝑁𝐶 ∗ − 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡 ∗
𝑑𝑁𝑇 ∗
= 0.004118𝑁𝐷 ∗ 𝑁𝐶 ∗
𝑑𝑡 ∗
This implies that all terms in the benzene disappearance equation are of equal importance.
Equation (4.1.8) becomes
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.
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 ∗ = etc. and 𝑡 ∗ = 1
𝐶𝐴𝑂 𝐶𝐴𝑂
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
𝑑𝑡
= −𝐾1 𝐶𝐴 − 𝐾2 𝐶𝐴 𝐶𝐵

𝑑𝐶𝐵
= 𝐾1 𝐶𝐴 − 𝐾2 𝐶𝐴 𝐶𝐵 + 2𝐾3 𝐶𝐴𝐵
𝑑𝑡
𝑑𝐶𝐶
= 𝐾1 𝐶𝐴 + 𝐾3 𝐶𝐴𝐵
𝑑𝑡
𝑑𝐶𝐴𝐵
= 𝐾2 𝐶𝐴 𝐶𝐵 − 𝐾3 𝐶𝐴𝐵
𝑑𝑡
Using dimensionless form
𝑑𝐶𝐴 ∗
𝐾1 𝐶𝐴𝑂 ∗
= −𝐾1 𝐶𝐴 ∗ 𝐶𝐴𝑂 − 𝐾2 𝐶𝐴 ∗ 𝐶𝐴𝑂 𝐶𝐵 ∗ 𝐶𝐵𝑂
𝑑𝑡

𝑑𝐶𝐴 ∗ 𝐾2
∗
= −𝐶𝐴 ∗ − ( 𝐶𝐴𝑂 ) 𝐶𝐴 ∗ 𝐶𝐵 ∗
𝑑𝑡 𝐾1
∗
𝑑𝐶𝐴
= −𝐶𝐴 ∗ − 𝛽𝐶𝐴 ∗ 𝐶𝐵 ∗
𝑑𝑡 ∗

𝑑𝐶𝐵 ∗ ∗ 𝐾2 ∗ ∗ 𝐾3
∗
= 𝐶 𝐴 − ( 𝐶𝐴𝑂 ) 𝐶𝐴 𝐶𝐵 + 2 ( ) 𝐶𝐴𝐵 ∗
𝑑𝑡 𝐾1 𝐾1
∗
𝑑𝐶𝐵
∗
= 𝐶𝐴 ∗ − 𝛽𝐶𝐴 ∗ 𝐶𝐵 ∗ + 2𝛼𝐶𝐴𝐵 ∗
𝑑𝑡

𝑑𝐶𝐶 ∗ ∗ 𝐾3
∗
= 𝐶𝐴 + ( ) 𝐶𝐴𝐵 ∗
𝑑𝑡 𝐾1
𝑑𝐶𝐶 ∗
∗
= 𝐶𝐴 ∗ + 𝛼𝐶𝐴𝐵 ∗
𝑑𝑡
 𝑑𝐶𝐴𝐵 ∗ 𝐾2 ∗ ∗ 𝐾3
∗
= ( 𝐶𝐴𝑂 ) 𝐶𝐴 𝐶𝐵 − ( ) 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
H2O2 -------------→ H2O
Notations used
H- heat of reaction (cal/mol)
k - reaction rate constant
C - concentration of hydrogen peroxide (mol/vol)
U - heat-transfer coefficient
A - heat-transfer area
TA-- average coolant temperature
F0- flow rate out of the reactor (vol/time)
To- inlet feed temperature
T- outlet temperature
Co- inlet peroxide concentration (mol/vol)
ρ – Density of fluid
QC- coolant flowrate (mass/time)
V- volume of the reactor

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 𝐹0 𝐶𝑝 (𝑇 − 𝑇0 )
𝑑𝑡

Assumptions
1)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

2) 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

C1 = Constant
The reaction rate constant follows the Arrhenius temperature dependency of
k = ko e -E/RT
k0 - frequency factor, a constant
E - activation energy

Information Flow diagram