L11-1

L1: Thermochemistry for

Nonisothermal Reactor Design
• The major difference between the design of isothermal and non-
isothermal reactors is the evaluation of the design equation
– What do we do when the temperature varies along the length of
a PFR or when heat is removed from a CSTR?
• Today we will start nonisothermal reactor design by reviewing
energy balances
• Next we will use the energy balance to design nonisothermal
steady-state reactors

Nonisothermal Energy balance

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-2

Why do we need to balance energy?

FA0 FA XA = 0.7

Arrhenius Eq
Consider an exothermic, liquid-phase reaction operated adiabatically in a
PFR (adiabatic operation- temperature increases down length of PFR):
k
A  B
dX A rA
Mole balance:  E
dV FA0 k  Ae RT
 E  1 1 
dX A k(1  X A ) dX A     (1  XA )
Rate law: rA  kCA R T T
   k1 exp   1  
dV 0 dV 0

Stoichiometry: FA  CA0 Need relationships: X T V

  0 We can get them from the energy balance
CA  CA0 (1  XA )
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-3

Clicker Question
The concentration of a reactant in the feed stream (inlet)
will be greatly influenced by temperature when the reactant is
a) a gas
b) a liquid
c) a solid
d) either a gas or a liquid
e) extremely viscous

Hints:
Liquid
 
C A0  j   j XA  P   T0 
Gas
phase:
Cj 
1   X A
  
 P0   T 
& solid C  C
phase:
j 
A0  j   j XA 

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-4

Thermodynamics in a Closed System

• First law of Thermodynamics
– Closed system: no mass crosses the system’s boundaries

Q

dEˆ   Q   W
W

dÊ: change in total energy of the system

dQ: heat flow to system
dW: work done by system on the surroundings

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-5

Thermodynamics in an Open System

• Open system: continuous flow system, 
Q
mass crosses the system’s boundaries
• Mass flow can add or remove energy Fin Fout

Hin Hout

Ẇ
Energy balance on system:

dEˆ sys n n
  W
 Q    FE   FE
i i in i i out
dt i1 i1
Rate of accum work energy added energy leaving
Heat
of energy in = - done by + to sys. by - sys. by mass
in
system system mass flow in flow out

Let’s look at these terms individually

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-6

The Work Term, Ẇ

dEˆ sys n n
  W
 Q    FE   FE
i i in i i out
dt i1 i1

Ẇ: Rate of work done by the system on the surroundings

• Work term is separated into “flow work” and “other work”.
• Flow work: work required to get the mass into and out of system
• Other work includes shaft work (e.g., stirrer or turbine)
n n
    FPV
W   FPV  
W Vi  specific volume
i i in i i out s
i1 i1  m3 
other work  
Flow work (shaft work)  mol of species i 
P : pressure
dEˆ sys n n
Plug in:   W
 Q    F E  PV    Fi Ei  PV i
s i i i in out
dt i1 i1
Energy &
Accum of energy = Heat - Other + work added - Energy & work
in system in work removed by flow out
by flow in
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-7

The Energy Term, Ei

Energy &
Accum of energy = Heat - Other + work added - Energy & work
in system in work removed by flow out
by flow in
dEˆ sys n n
  W
 Q    F E  PV    Fi Ei  PV i
s i i i in out
dt i1 i1

ui2
Ei  Ui   gzi  other
2 Electric, magnetic,
light, etc.
Internal energy Potential energy
Kinetic energy
ui2
Usually: Ui   gzi  other Ei  Ui
2 Internal energy is major
contributor to energy term
dEˆ sys n n
Plug in Ui for Ei:  -W
Q    F (U  PV ) -  F (U  PV )
s i i i in i i i out
dt i1 i1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-8

Total Energy Balance

dEˆ sys n n
 -W
Q    F (U  PV ) -  F (U  PV )
s i i i in i i i out
dt i1 i1

Hi  Ui  PVi Recall eq for enthalpy, a

function of T
unit : (cal / mole)

dEˆ sys n n
 W
Q    FH   FH
s i i in i i out
dt i1 i1

n n
Steady state:  W
0Q    F H   FH
s i0 i0 i i
i1 i1

Accumulation = 0 = in - out + flow in – flow out

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-9

In Terms of Conversion:
n n
Steady state:  W
0Q    F H   FH
s i0 i0 i i
i1 i1
Fi0
Fi  Fi0   iFA0 XA  Fi  FA0  i   i XA  where i 
FA0
dEˆ sys n n
If XA0=0, then:  W
Q    H  F   H F    X 
s i0 i A0 i A0 i i A
dt i1 i1
Multiply dEˆ sys  
n n
 Q  Ws   Hi0 iFA0   HiFA0 i  HiFA0 i XA 
out: dt i1 i1

Total energy dEˆ sys n n

  Hi0  Hi  i    iHi FA0 XA
balance (TEB)  dt  Q  Ws  FA0 i
1 i1 i
n
Relates temperature to XA   iHi  HRX  T   heat of rxn at temp T
i1

dEˆ sys n
Must use this
  W
Q   F   H  H   H  T  F X equation if a phase
s A0 i i0 i RX A0 A
dt i1 change occurs
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-10

What is (Hi0 – Hi)?

dEˆ sys n
 W
Q   F   H  H   H  T  F X
s A0 i i0 i RX A0 A
dt i1
What is the heat of reaction for species i (Hi)?
heat of reaction Hi  Hi  TR   HQi

Enthalpy of formation of i at Change in enthalpy due to

reference temp (TR) of 25 °C heating from TR to rxn temp T
When NO phase change occurs H  T2 C dT  C T  T 
Qi T pi pi R
& heat capacity is constant: 1

 Hi  Hi  TR   Cpi T  TR 

  
Hi0  Hi  Hi  TR   Cpi Ti0  TR   Hi  TR   Cpi T  TR  
 Hi0  Hi  Cpi Ti0  TR   Cpi T  TR 

 Hi0  Hi  Cpi Ti0  Cpi TR  Cpi T  Cpi TR

 Hi0  Hi  Cpi Ti0  Cpi T  Hi0  Hi  Cpi  Ti0  T 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-11

What is ΔHRX(T)?
dEˆ sys n
 W
Q   F   H  H   H  T  F X
s A0 i i0 i RX A0 A
dt i1
How do we calculate ΔHRX(T), which is the heat of reaction at temperature T?
b c d
For the generic reaction: A  B  C  D
a a a
d c b
HRX  T   HD  HC  HB  HA where Hi  Hi  TR   Cpi T  TR 
a a a
d c b  d c b 
 HRX  T    HD  TR   HC TR   HB TR   H A  TR    CPD  CPC  CPB  CPA   T  TR 
a a a  a a a 
d  c b
HRX  TR   H D  TR   HC  TR   HB  TR   H A  TR 
a a a
d c b
CP  CPD  CPC  CPB  CPA
a a a

 HRX  T   HRX  TR   CP  T  TR 

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-12

Example: Calculation of ΔHRX(T)

For the reaction N2 (g) + 3H2 (g) → 2NH3 (g), calculate the heat of reaction
at 150 °C in kcal/mol of N2 reacted.
Extra info:  HN2

 TR   0 HH2

 TR   0 HNH3  TR   11,020cal mol


cal cal cal

CPH  6.992 CPN  6.984 CPNH  8.92
2
molK 2
molK 3
molK
HRX  T   HRX  TR   CP  T  TR 
d  c b
HRX  TR   H D  TR   HC  TR   HB  TR   H A  TR 
a a a
1N2  3H2  2NH3 a 1 b3 c 2 d0
2 cal  3 cal
TR    11,020   0   0 RX  R 

H 
RX
 H T  22,040
1 mol  1 mol N2 reacted
d c b
CP  CPD  CPC  CPB  CPA
a a a
2 3  cal cal
 CP   8.92   6.992   6.984   CP  10.12
1 1  mol N2 reactedK mol N2 reactedK
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-13

Example: Calculation of ΔHRX(T)

For the reaction N2 (g) + 3H2 (g) → 2NH3 (g), calculate the heat of reaction
at 150 °C in kcal/mol of N2 reacted.
Extra info: H N2

 TR   0 HH2

 TR   0 HNH3  TR   11,020cal mol


cal cal cal

CPH  6.992 CPN  6.984 CPNH  8.92
2
molK 2
molK 3
molK
HRX  T   HRX  TR   CP  T  TR 
cal cal
HRX  TR   22,040 CP  10.12
mol N2 reacted mol N2 reactedK

Convert T and TR to Kelvins

T  150 C  150  273 K  423K TR  25 C   25  273 K  298K
cal  cal 
HRX  T   22,040   10.12   423K  298K 
mol N2 reacted  mol N2 reactedK 
cal kcal
 HRX  T   23,310  23.31
mol N2 reacted mol N2 reacted
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-14

Example: Calculation of ΔHRX(T)

For the reaction N2 (g) + 3H2 (g) → 2NH3 (g), calculate the heat of reaction
at 150 °C in kJ/mol of H2 reacted.
Extra info: H N2

 TR   0 HH2

 TR   0 HNH3  TR   11,020cal mol


cal cal cal

CPH  6.992 CPN  6.984 CPNH  8.92
2
molK 2
molK 3
molK
HRX  T   HRX  TR   CP  T  TR 
cal cal T  423K
H 
RX TR   22,040 CP  10.12
mol N2 reactedK TR  298K
mol N2 reacted
kcal
HRX  T   23.31 Convert kcal to kJ
mol N2 reacted
23.31 kcal  4.184 kJ  kJ
 HRX  T    HRX  
T  97.53
mol N2 reacted  kcal  mol N2 reacted
Put in terms of moles H2 reacted 1N2  3H2  2NH3
kJ  1 mol N2  kJ
 HRX  T   97.53     HRX  T   32.5
mol N2 reacted  3 mol H2  mol H2 reacted
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-15

Q and Hi in Terms of T
• Ignore enthalpy of mixing (usually an acceptable assumption)
• Look up enthalpy of formation, Hi◦(TR) in a thermo table, where the
reference temperature TR is usually 25◦C
• Compute Hi(T) using heat capacity and heats of vaporization/melting
no phase change: Hi  Hi (TR )  TT CpidT
R
n n n
 T  
 
HRX T    iHi    iHi (TR )  T    iCpi dT
R i1
i1 i1 
Tm T
Phase change at Tm H T  H  T   C dT  H   C dT
   
i i R psi m,i pli
(solid to liquid): Solid at T TR Tm
R
Cpsi : heat capacity of solid Cpli : heat capacity of liquid
Hm,i : enthalpy of melting

melting For Tm < T < Tb ←boiling

If constant of average heat capacities are used, then:
  T  T   H  C
Hi  T   Hi  TR   C   T  T  For T < T < T
psi m R m,i pli M m b

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-16

Insert ΔHRX(T) & (Hi0 – Hi) into EB

b c d dEˆ sys n
A  B  C D  W
Q   F   H  H   H  T  F X
a a a s A0 i i0 i RX A0 A
dt i1
HRX  T   HRX  TR   CP  T  TR  Hi0  Hi  Cpi  Ti0  T 
dEˆ sys n

dt
 W
Q A0 i pi i0
i1
RX R P 
  F   C  T  T   H  T   C  T  T  F X
s R A0 A 
(Ti0 – T) = - (T – Ti0)
dEˆ sys n

dt
 W
Q s A0 i pi
i1
i0 RX R P 
  F   C  T  T   H  T   C  T  T  F X
R A0 A 
Example calculations of ∆H°RX(TR) &
ΔCp are shown on the previous slides
n Fi0
 iCpi  CpA  B CpB  C CpC  D CpD where i 
i1 FA0
If the feed does not contain   FC0  0 &   FD0  0
C D
the products C or D, then: FA0 FA0
n
  iCpi  CpA  B CpB
i1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-17

Clicker Question
dEˆ sys n

dt
 W
Q i pi i0
i1
RX R P R
  F   C  T  T   H  T   C  T  T  F X
s A0 A0 A 
Accum of Energy &
energy in = Heat Other Energy & work
- + work added -
system in work removed by flow out
by flow in

If the reactor is at a steady state, which term in this equation would be zero?
a) dEsys/dt

b) Q
c) Ẇ
d) FA0
e) ∆CP
At the steady state:
n
 W
0Q i pi i0
i1
RX R P 
  F   C  T  T   H  T   C  T  T  F X
s A0 R A0 A 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-18

How do we Handle Q in a CSTR?

CSTR with a heat exchanger, perfectly mixed inside and outside of reactor

FA0

  UA(T  T)
Q Ta
a Ta
T, X

T, X
The heat flow to the reactor is in terms of:
• Overall heat-transfer coefficient, U
• Heat-exchange area, A
• Difference between the ambient temperature in the heat jacket, Ta, and
rxn temperature, T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L11-19

Tubular Reactors (PFR/PBR):

Integrate the heat flux equation along the length of the
reactor to obtain the total heat added to the reactor :
   A U(T  T)dA   V Ua(T  T)dV
Q a a

a: heat-exchange area per unit volume of reactor

A
a
V


dQ Heat transfer to a perfectly mixed PFR in a jacket
 Ua(Ta - T)
dV For a tubular reactor of diameter D, a = 4 / D

For a jacketed PBR (perfectly mixed in jacket):

 dQ
1 dQ  Ua
  (Ta  T) Heat transfer to a PBR
b dV dW b
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.