Plug flow is a simplified and idealized picture of the

motion of a fluid, whereby all the fluid elements

move with a uniform velocity along parallel
streamlines.
This perfectly ordered flow is the only transport
mechanism accounted for in the plug flow reactor
model.
Because of the uniformity of conditions in a cross
section the steady-state continuity equation is a very
simple ordinary differential equation.

z=0

z + z

z=L

MASS BALANCE
Rate of flow
of A into a
volume
element

FA V

Rate of
generation of A by
chemical reaction
within the volume
element

rA V

dNA
0
For steady-state process:
dt
FA V rA V FA V V 0
FA V V FA V rA V

Rate of flow
of A out of
the volume
element

FA V V

Rate of
accumulation
of A within
the volume
element

dNA
dt

FA V V FA V rA V
FA V V FA V
rA
V
FA z z FA z

rA A
lim
z 0
z

dFA
rA
dV

By definition of the conversion

FA FA 0 1 X
dFA FA 0 dX

So that the continuity for A becomes:

FA 0 dX rA dV

dV FA 0

dX rA

Design equation

(1.1)

To design an isothermal tubular/plug-flow reactor, the

following information is needed:
1. Design equation
dV FA 0

dX rA

(1.1)

2. Rate law
rA k C A

(for first order reaction)

(1.2)

3. Stoichiometry (liquid phase)

C A C A 0 1 X

(1.3)

Combining eqs. (1.2) and (1.3) yields:

rA k C A 0 1 X

(1.4)

Introducing eq. (1.4) into eq. (1.1) yields:

V X
dX
1
X

ln1 X X
FA 0 X kC A 0 1 X
k CA0

FA 0 1 X FA 0 1 X 0

V
ln
ln

kC A 0 1 X 0 kC A 0 1 X
v0 1 X v0 1 X0
ln
V ln

k 1 X0 k 1 X

To design an isothermal tubular/plug-flow reactor, the

following information is needed:
1. Design equation
dV FA 0

dX rA

(1.1)

2. Rate law
rA k C A

(for first order reaction)

(1.2)

3. Stoichiometry (liquid phase)

C A C A 0 1 X

(1.3)

Combining eqs. (1.1), (1.3), and (1.4) yields:

dX kC A 0 1 X k 1 X

dV
FA 0
v0

(1.5)

Recalling the Arrhenius equation:

E 1 1
k k 1 exp
R T1 T

(1.6)

Combining eqs. (1.5) and (1.6) yields:

E 1 1
dX k 1
1 X exp
dV
v0
T T1 T

(1.7)

In a closed system, the change in total energy of the system,

dE, is equal to the heat flow to the system, Q, minus the
work done by the system on the surrounding, W.
S
W

in 0
m

out 0
m
Q

Thus the energy balance for a closed system is:

dE Q W

(1.8)

Open system:
S
W

Fi in

Fi out

Hi in

Hi out

For an open system in which some of the energy exchange

is brought about by the flow of mass across the system
boundaries, the energy balance for the case of only one
species entering and leaving becomes:
Rate of
accumulation of
energy
within the
system

Rate of flow
of heat to
the system
from the
surrounding

Rate work
done by the
system on
the
surrounding

dEsys
Fin Ein Fout Eout
Q W
dt

Rate of
energy added
to the system
by mass flow
into the
system

Rate energy
leaving
system by
mass flow out
of the system

(1.9)

The unsteady-state energy balance for an open system

that has n species, each entering and leaving the system at
its respective molar flow rate Fi (mole of i per time) and
with its respective energy Ei (joules per mole of i), is:
n
n
dEsys
Ei Fi Ei Fi
Q W
i 1
i 1
dt
in
out

(1.10)

 , into:
It is customary to separate the work term, W

flow work: work that is necessary to get the mass into

and out of the system
S.
other work / shaft work, W

For example, when shear stresses are absent:

n

i 1

i 1

FiPVi FiPVi
W
in

S
W

(1.11)

out

Stirrer in a CSTR
Turbine in a PFR

[rate of flow work]

where P is the pressure and Vi is the specific volume.

Combining eqs. (1.10) and (1.11) yields:

n
n
dEsys
S Fi Ei PVi Fi Ei PVi
Q W
i 1
i 1
dt
in
out

(1.12)

The energy Ei is the sum of the internal energy (Ui), the

kinetic energy u2i 2 , the potential energy (gzi), and any
other energies, such as electric energy or light:
u2i
Ei Ui gzi other
2

(1.13)

In almost all chemical reactor situations, the Kinetic,

potential, and other energy terms are negligible in
comparison with the enthalpy, heat transfer:
Ei Ui

(1.14)

Recall the definition of enthalpy:

Hi Ui PVi

(1.15)

Combining eqs. (1.16), (1.15), and (1.13) yields:

n
n
dEsys
S Fi Hi Fi Hi
Q W
i 1
i 1
dt
in
out

(1.16)

We shall let the subscript 0 represent the inlet

conditions. The un-subscripted variables represent the
conditions at the outlet of the chosen system volume.
n
n
dEsys
S Fi0 Hi0 Fi Hi
Q W
i 1
i 1
dt

(1.17)

The steady-state energy balance is obtained by setting

(dEsys/dt) equal to zero in eq. (1.17) in order to yield:
n

S Fi0 Hi0 Fi Hi 0
Q W
i 1

i 1

(1.18)

To carry out the manipulations to write eq. (1.18) in

terms of the heat of reaction we shall use the
generalized reaction:
A bB c C dD

(1.19)

The inlet and outlet terms in Equation (1.19) are

expanded, respectively, to:
In:

Hi0Fi0 HA 0FA 0 HB 0FB 0 HC 0FC 0 HD 0FD0 HI0FI0

Out: HiFi HAFA HBFB HCFC HDFD HIFI

(1.20)
(1.21)

We first express the molar flow rates in terms of conversion

FA FA 0 1 X

(1.22)

FB 0

FB FB 0 b FA 0 X FA 0 b X
FA 0

FB FA 0 B b X

(1.23)

 FC 0

FC FC 0 c FA 0 X FA 0 c X
FA 0

FC FA 0 C c X

(1.24)

FD FA 0 D d X

(1.25)

FI0
FI FI0 FA 0 FA 0 I
FA 0

(1.26)

Substituting eqs. (1.23) (1.27) into eq. (1.22) gives:

HiFi HAFA 0 1 X HBFA 0 B bX

HCFA 0 C c X HDFA 0 D dX HIFA 0 I

(1.26)

Subtracting eqs. (1.26) from eq. (1.20) gives:

Hi0Fi0 HiFi FA 0 HA 0 HA HB 0 HB B
n

i 1

i 1

FA 0 HC 0 HC C HD 0 HD D HI0 HI I
dHD c HC bHB HA FA 0 X

(1.27)

The term in parentheses that is multiplied by FA0X is called

the heat of reaction at temperature T and is designated
HRx.
HRx dHD T c HC T b HB T HA T

(1.28)

All of the enthalpies (e.g., HA, HB) are evaluated at the

temperature at the outlet of the system volume, and
consequently, [HRx(T)] is the heat of reaction at the
specific temperature ip: The heat of reaction is always
given per mole of the species that is the basis of
calculation [i.e., species A (joules per mole of A reacted)].

Substituting eq. (1. 28) into (1. 27) and reverting to

summation notation for the species, eq. (1. 28) becomes

Hi0Fi0 HiFi FA 0 i Hi0 Hi HRxFA 0 X

n

i 1

i 1

i 1

(1.29)

Substituting eq. (1.29) into (1.18) yields:

S FA 0 i Hi0 Hi HRxFA 0 X 0
Q W
n

i 1

(1.30)

 The enthalpy changes on mixing so that the partial molal

enthalpies are equal to the molal enthalpies of the pure
components.
The molal enthalpy of species i at a particular temperature
and pressure, Hi, is usually expressed in terms of an
enthalpy of formation of species i at some reference
temperature TR, Hi(TR), plus the change in enthalpy that
results when the temperature is raised from the reference
temperature to some temperature T, HQi
Hi Hi0 TR HQi

(1.31)

The reference temperature at which Hi is given is usually

25C. For any substance i that is being heated from T1 to T2 in
the absence of phase change
T2

HQi CP dT
T1

(1.32)

A large number of chemical reactions carried out in

industry do not involve phase change. Consequently, we
shall further refine our energy balance to apply to singlephase chemical reactions. Under these conditions the
enthalpy of species i at temperature T is related to the
enthalpy of formation at the reference temperature TR by
T

Hi H TR CpidT
0
i

TR

(1.33)

The heat capacity at temperature T is frequently expressed in a

quadratic function of temperature, that is,
Cpi i i T i T 2

(1.34)

To calculate the change in enthalpy (Hi Hi) when the reacting

fluid is heated without phase change from its entrance
temperature Ti0 to a temperature T, we use eq. (1.33)
T
T
0
0

Hi Hi0 Hi TR CpidT Hi TR CpidT

T
T

i0

Hi Hi 0 CpidT
Ti 0

(1.35)

Introducing eq. (1.35) into eq. (1.30) yields:

n T

S FA 0 iCpidT HRxFA 0 X 0
Q W
i1 Ti 0

(1.36)

The heat of reaction at temperature T is given in eq. (1.28):

HRx dHD T c HC T b HB T HA T

(1.28)

where the enthalpy of each species is given by eq. (1.33):

T

Hi H TR CpidT
0
i

TR

(1.33)

If we now substitute for the enthalpy of each species, we have

HRx dHD0 TR cH0C TR bHB0 TR H0A TR
dCpD cCpC bCpB CpA dT
T

TR

(1.37)

The first set of terms on the right-hand side of eq. (1.37) is

the heat of reaction at the reference temperature TR,
0
TR dHD0 TR c H0C TR bHB0 TR H0A TR
HRx

(1.38)

The second term in brackets on the right-hand side of eq.

(1.37) is the overall change in the heat capacity per mole of A
reacted, Cp,
Cp dCpD cCpC bCpB CpA

(1.39)

Combining Equations (1.38), (1.39), and (1.37) gives us

HRx T H

0
Rx

TR CpdT
TR

(1.40)

The heat flow to the reactor, Q , is given in terms of the overall

heat-transfer coefficient, U, the heat-exchange area, A, and
the difference between the ambient temperature, Ta, and the
reaction temperature, T.
When the heat flow vanes along the length of the reactor,
such as the case in a tubular flow reactor, we must integrate
the heat flux equation along the length of the reactor to
obtain the total heat added to the reactor,
A

Q UTa T dA Ua Ta T dV
0

(1.41)

where a is the heat-exchange area per unit volume of reactor.

The variation in heat added along the reactor length (i.e.,

volume) is found by differentiating with respect to V:
dQ
Ua Ta T
(1.42)
dV
For a tubular reactor of diameter D, a = D/4
For a packed-bed reactor, we can write eq. (1.43) in terms of
catalyst weight by simply dividing by the bulk catalyst
density
1 dQ Ua
Ta T
B dV B

Recalling dW = B dV, then

dQ Ua
Ta T
dW B

(1.43)

Substituting eq. (1.40) into eq. (1.36), the steady-state energy

balance becomes
T

Q WS FA 0 iCpidT HRx TR Cp dT FA 0 X 0
i 1 T
T

n T

i0

(1.44)

For constant of mean heat capacity:

S H TR C p T TR FA 0 X FA 0 iC pi T Ti0
Q W
0
Rx

i 1

(1.45)

EXAMPLE 1.1
Calculate the heat of reaction for the synthesis of ammonia
from hydrogen and nitrogen at 150C in kcal/mol of N2
reacted.

SOLUTION
Reaction:

N2 + 3H2 2NH3

0
0
TR 2HNH
TR 3HH0 TR HN0 TR
HRx
3

= 2 ( 11.02) 3 (0) 0 = 20.04 kcal/mol N2

Cp 6.992 cal mol H2 .K
H2

Cp 6.984 cal mol N2 .K

N2

Cp

NH3

8.92 cal mol NH3 .K

C p 2C p

NH3

3C p C p
H3

N2

= 2 (8.92) 3 (6.992) 6.982

= 10.12 cal/mol N2 reacted . K
0
TR C p T TR
HRx T HRx

HRx 423 22.04 10.12 423 298

= 23.21 kcal/mol N2