Chapter 9 Energy balance for

reactive processes
Heat of reaction
Hess’s Law
Heat of formation
Heat of combustion
Energy balance calculation for reactive
process

1
9.1 Heat of Reaction:
^
2 H 2 +O 2 → 2 H 2O + ∆ H r (T , P)
– Energy is REQUIRED to break bonds of reactants
– Energy is RELEASED when product formed.
– Exothermic reaction
Heat released > Heat required:
 Heat rejected to surroundings

– Endothermic reaction
Heat required > Heat Released:
 Heat supply from surroundings needed
2
The Activation Energy for Chemical
Reaction

A+BC
Energy
Level Activation
energy

Heat of
A+B reaction

Time
3
• Heat of reaction (definition):
^
Heat (enthalpy) of reaction, ∆ H r (T , P) , is the
enthalpy change for a process in which
stoichiometric quantities of reactants at (T,P) react
completely in a single reaction to form products at
the same (T,P).

Example: C C ( s ) + 2 H O → C (OH ) + C H ( g )
a 2 2 a 2 2 2

^
∆ H r (250 C ,1atm) = H prod − H reac
= −125.4 kJ / mol
4
The standard state is: (25ºC, 1 atm), the standard
heat of reaction is denoted as:
^ ^ 0
∆Hr = ∆Hr 25ºC, 1 atm

For a reaction: 2A + B  3C

^
∆ H r (100 C ,1atm) = −50 kJ / mol
0

Means: − 50 kJ − 50 kJ − 50 kJ
= =
2 mol A 1 mol B 3 mol C generated
5
• If 150 mol C/s is generated in the given
condition, the associated enthalpy change is:
• − 50 kJ
∆ H = 150 ×
3 mol C generated
= −2,500 kJ / s
consumed
More generally:
^
∆ H r (T0 , P0 )
∆H = × n A, r
νA
νA : Stoichiometric
coefficient of A
6
• The extent of reaction, ξ ,

n A,out − nin n A, r
ξ= = (Chapter 4)
νA νA

ξ , a measure of how far a reaction has

proceeded.

• For a reaction @ (T0,P0) with reaction extent, ξ

the change of enthalpy is:
^
∆H = ξ × ∆ H r (T0 , P0 )
7
 ^
∆ H r (T , P) < 0 The reaction is exothermic @ (T,P)
^
∆ H r (T , P) > 0 The reaction is endothermic @ (T,P)
^
Heat of reaction, ∆ H r (T , P)

• (1) nearly independent of P (at medium low

pressure),  a function of T.
• (2) depends on how the stoichiometric equation
is written, ^
2 H 2 +O 2 → 2 H 2 O + ∆ H r (T , P )
^
H 2 + 1 / 2O 2 → H 2O + 1 2 ∆ H r (T , P )
8
 ^
Heat of reaction, ∆ H r (T , P)

•(3) Depends on the state of aggregation of

reactants and products
^
2 H 2 +O 2 → 2 H 2O ( g ) + ∆ H r (T , P)
^
2 H 2 +O 2 → 2 H 2O(l ) + ∆ H 2 r (T , P )

• (4) Relates to Internal energy change of

a reaction
 
^ ^  
∆ U r (T ) = ∆ H r (T ) − RT  ∑ ν i − ∑ ν i 
 gaseous gaseous 
 products reac tan ts  9
How to measure a heat of reaction?

• Calorimeter
– A closed reactor immersed in
a fluid and contained in well
insulated vessel
– Has a lot of constraints, e.g.
C(s) + ½ O2  CO (g)

(low rate of reaction, difficult to control)

But there is an easy solution,,,

10
9.2 Hess’s Law

• If the stoichiometric equation for 1 can be obtained

by algebraic operations (multiplication by constants,
addition, and subtraction) on stoichiometric
equations for reaction 2, 3 ,,,
^ 0
then the heat of reaction, ∆ H r 3 , can be obtained
by performing the same operations on the heats of
^ 0 ^ 0
reactions, ∆ H r1 , ∆ H r 2 ...

11
Example of Hess’s law
^ 0
C + O2  CO2 eq(1) ∆ H r1 = −393.51 kJ / mol
^ 0
CO + ½ O2  CO2 eq(2) ∆ H r 2 = −282.99 kJ / mol
^ 0
C + ½ O2  CO eq(3) ∆ H r3 = ?

With Hess’s Law:

as eq(3) = eq(1) – eq(2)
^ 0 ^ 0 ^ 0
∆ H r 3 = ∆ H r1 − ∆ H r 2 = −393.51 + 282.99
= −110.52 kJ / mol
12
 ^
2 H 2 +O 2 → 2 H 2O ( g ) + ∆ H 1r (T , P )
^
2 H 2 +O 2 → 2 H 2O (l ) + ∆ H 2 r (T , P )
^ ^
What’s the physical significance of ∆ H 1r (T , P ) − ∆ H 2 r (T , P ) ?

19 ^
C6 H14 (l ) + O 2 → 6CO2 ( g ) + 7 H 2O (l ) + ∆ H 1r (T , P )
2
19 ^
C6 H14 ( g ) + O 2 → 6CO2 ( g ) + 7 H 2O (l ) + ∆ H 2 r (T , P )
2

What’s the heat of vaporization of C6H14?

13
9.3 Formation reaction & Heats of formation
• Formation reaction:
– A compound is formed by elemental constituents
as they normally occur in nature (e.g. O2, N2,
instead of O, N)

^ 0

• Standard heat of formation, ∆ H f

– Enthalpy change associated with the formation
of 1 mole of the compound at the reference state
(T= 25ºC, P = 1atm)
14
•Determine heat of reaction from heat of formation
With Hess’s Law:
^ 0 ^ 0 ^ 0
∆Hr = ∑ν
products
i ∆ H fi − ∑ν
reac tan ts
i ∆H fi

Standard heats of formation of all elemental

species are ZERO

Example: Determine the standard heat of

reaction from the combustion of liquid n-pentane,
(using heat of formation in Table B.1):
C5H12 (l) + 8 O2 (g) 5 CO2 (g) + 6H2O (l)

15
Solution:
^ 0
∆Hr =
^ 0 ^ 0
∑γ H
product
f − ∑γ H
reac tan t
f

 ^0   ^0   ^0 
5 ∆ H f  + 6 ∆ H f  −  ∆ H f 
 CO2 ( g )   H 2O ( l )  C5 H12 (l )
= −3509 kJ / mol

 ^0 
Note:  ∆ H f  = 0
 O2
16
To verify the formula, we may use Hess’s law:
^ ^
5C ( s ) + 6 H 2( g ) → C5 H12 (l ), ∆ H 0 1r = ( ∆ H 0 f )C5H12 ( l ) (1)

^ ^
C ( s ) +O 2 ( g ) → CO2 ( g ), ∆ H 0
2r = ( ∆ H 0 f )CO2 ( g ) (2)
^ ^
1
H 2 ( g ) + O 2 ( g ) → H 2O (l ), ∆ H 0 3r = ( ∆ H 0 f ) H 2O ( l ) (3)
2
5 eq (2)+6 eq (3) – eq (1)

C5H12 (l) + 8 O2 (g) 5 CO2 (g) + 6H2O (l)

^ ^ ^
5( ∆ H 0 f )CO2 ( g ) + 6( ∆ H 0 f ) H 2O ( l ) − ( ∆ H 0 f )C5H12 ( l )

17
 ^ 0
9.4 Standard heat of combustion ∆ H C
• Heat of combustion of that substance with O2 to
yield specific products [CO2(g) and H2O(l)] with
both reactants and products at 25ºC, 1 atm.
– Assumptions:
(1) all C in the fuel forms CO2 (g),

(2) all H Forms H2O (l),

(3) all S forms SO2(g), and
(4) all N form N2(g).

Standard heat of combustion is listed in Table B.1.

^ 0 ^ 0
C2H5OH (l) + 3O2 (g) ∆ H C = ∆ H r = −1366.9 kJ / mol
18
2CO2 (g)+3H2O (l)
• Heating values (of fuel)
– Negative of the standard heat of combustion
(HV>0)
^ 0
– Higher heating value: HHV = − H C with H2O (l)
as product
– Lower heating value (LHV): based on H2O (v)
as product
^
HHV = LHV + n∆ H V ( H 2O, 25C )
^
∆ H V ( H 2O,25C ) = 44.013 kJ / mol
19
– For a mixture of fuels:

HV = ∑ xi ( HV ) i

xi == Molar or mass fraction of component i

Table: Heating values (Unit: kJ/mol)

H2 C CH4 C8H18
285.84 393.51 890.36 5470.7

H2 is a much better fuel, why ???

20
• Example: calculate heating value

– Natural gas contains 85% methane and 15%

ethane by volume. The heats of combustion @
25C, 1atm with water vapor are given below:
CH4 + 2O2(g)  CO2(g) +2H2O(v)
^ 0
∆ H c = −802 kJ / mol
C2H6 + 3.5O2(g)  2CO2(g) +3H2O(v)
^ 0
∆ H c = −1428 kJ / mol
Calculate the higher heating value of the natural
gas.
21
Solution:
^
( HHV ) CH 4 = ( LHV )CH 4 + nH 2O (∆ H V ) H 2O
= 802 + 2 × 44.013 = 889.6 kJ / mol
( HHV )C2 H 6 = 1428 + 3 × 44.013 = 1560 kJ / mol

HHV = ∑ xi ( HV )i
= 0.85 X 889.6 + 0.15 X 1560 = 990.16kJ / mol

22
 ^ 0
•Calculate heat of reaction, ∆ H r , from heat of
^ 0
combustion, ∆ H C , (using Hess’s Law)

If a reaction involves only combustible

substances and combustible products, its
^ 0
standard heat of reaction, ∆ H r , can be
calculated from the tabulated standard heat of
combustion ∆ H^ C0 .
^ 0 ^ 0 ^ 0 ^ 0
∆ H r = −∑ ν i ∆ ( H c ) i = ∑ν i ∆ ( H c )i − ∑ν i (∆ H c )i
i reac tan ts products

product
reactant 23
 ^ 0 ^ 0 ^ 0 ^ 0
∆ H r = −∑ ν i ∆ ( H c ) i = ∑ν i ∆ ( H c )i − ∑ν i (∆ H c )i
i reac tan ts products

• Which assumes a hypothetical path with:

– (1) all combustible reactants are burned with

O2 at 25C,
– (2) CO2 and H2O combine to form reaction
products and O2, (reverse of combustion
reaction)
– negative sign (different from the Heat of
^ 0
formation ∆ H f )
24
• Example: C2H6  C2H4 + H2
^ 0
∆Hc C2H6 C2H4 H2
kJ/mol -1559.9 -1411.0 -285.8

^ 0 ^ 0
∆ H r = −∑ ν i ∆ ( H c ) i
i
^ 0 ^ 0
= ∑ν
reac tan ts
i ∆ ( H c )i − ∑ν
products
i (∆ H c )i

^ 0 ^ 0 ^ 0 ^ 0
∆ H r = (∆ H c ) C2 H 6 − (∆ H c ) C2 H 4 − (∆ H c ) H 2
= 136.9 kJ / mol
25
Hess law and Hypothetical path
C2H4 + 6/2O2  2CO2 + 2H2O (1)
H2 + 1/2O2  H 2O (2)

C2H6 + 7/2O2  2CO2 + 3H2O (3)

26
 ^ 0
• Application of heat of combustion ∆ H c :
– To determine the heat of formation for combustible
substances whose formation reaction do not occur
naturally.
E.g. determine the heat of formation of pentane:
^ 0
5C(s) + 6H2  C5H12 (l) ∆H f =?
Note: (1) Very difficult to have such an experiment
(2) All elements are combustible and their heat of
combustion can be determined experimentally, so
^ 0 ^ 0 ^ 0 ^ 0
(∆ H f ) C5 H12 (l ) = 5(∆ H c ) C ( s ) + 6(∆ H c ) H 2 ( g ) − (∆ H c ) C5 H12 (l )

Table B.1 27
28
9.5 Energy balance on reactive processes
9.5a General procedures
– 5 steps, Similar to those used in Chapter 8

• (1) draw & label flow chart and do material

balance,
• (2) choose reference state,
• (3) setup overall energy balance equation,
• (4) Inlet-Outlet enthalpy Table,
• (5) calculate ΔH, or ΔU
29
Two approaches for the reaction process

(1)heat of reaction method:

^
for single reaction for which ∆ H r is
known.

(2) heat of formation method

for multiple reactions, or single reaction

^
for which ∆ H r is unavailable

30
Example of application (using both methods):

100 mol O2 (g)/s

100 mol C3H8 (g)/s, 25ºC
2256 mol N2(g)/s
Furnace
300 mol CO2(g)/s
600 mol O2(g)/s, 300ºC 400 mol H2O(v)/s
Q kJ/s
2256 mol N2 (g)/s 1000ºC
????

C3 H 8 + 5O2 → 2CO2 ( g ) + 4 H 2O(l )

^ 0
∆ H r = −2220 kJ / mol

31
-Choosing reference state
• Reference State: @ 25C, 1 atm, molecular species

O2, N2, CO2, H2O,

O2, N2 300 ˚ C
1000 ˚ C 1 atm

25C, 1atm
^ 0
∆Hr O2, N2, CO2, H2O,
25 ˚ C 1 atm
C3H8 , 1atm 25 ˚ C,
H=0 C3 H 8 + 5O2 → 2CO2 ( g ) + 4 H 2O(l )
^ 0
∆ H r = −2220 kJ / mol
32
(1) Heat of reaction method (considering heat of reaction
explicitly)
(a) Material balance -- done on flow chart
(b) Reference -- 25ºC, 1atm, molecular species

(c) Calculate -- the extent of reaction, ξ

 •   • 
 nC3 H 8  −  nC3 H 8 
•
  out  in 0 − 100
ξ= = = 100 mol / s
νC H 3 8
1

33
(d) Prepare inlet-outlet enthalpy table

(reference: C3H8(g), H2O(l), CO2, O2, N2, @ 25C,

1atm)
• • ^
^
n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol
C3H8 100 0 -- --
^ ^
O2 600 H2 100 H4
^ ^
N2 2256 H3 2256 H5 ^
CO2 -- -- 300 H6
^
H2O -- -- 400 H7
34
 ^
(e) Calculate the unknown enthalpy H i
^ ^
Table B.8 H 2 = ∆ H [O2 (25C ) → O2 (300C )]
O2 = 8.47 kJ / mol
^
N2 H 3 = 8.12 kJ / mol ,
^
O2
H 4 = 32.47 kJ / mol ,
^
N2 H 5 = 30.56 kJ / mol
^
CO2 H 6 = 48.60 kJ / mol ,
^ ^ 1000
H2O (25 1000)
H7 = Hv+ ∫ C p dT = 44.02 + 37.69
Can use steam table 25

= 81.71 kJ / mol 35
 •
(f) Calculate ∆ H for the reactor
• • ^ 0 • • • •
∆ H = ξ ∆ H r + ∑ n out H out − ∑ n in H in

−5
Chemical reaction
= −1.26 ×10 kJ / s

(g) Overall energy balance

• • • • •
Q+ W s = ∆ H + ∆ E K + ∆ E P

37
(2) Heat of formation method:

(a) Material balance -- done on flow chart

(b) Reference state for enthalpy calculation
-- (Different from last method!)
(i) Reacting species: Elemental species ,
which constitute the reactant and product
@ 25C, 1 atm
 C(s), H2(g), O2(g), @ 25C, 1atm
(ii) Non-reacting species: at any convenient
temperature
 N2 (g), @ 25C, 1atm 38
 Diagram for Reference of Elemental species ,@
25C, 1 atm,  C(s), H2(g), O2(g), @ 25C, 1atm

O2, N2, 1000 ˚ C

O2, N2
1 atm
300˚ C
CO2, H2O,
C3H8 , 1atm C p dT 1000 ˚ C, 1 atm
25 ˚ C C p dT
^ 0
∆ H f + C p dT
^ 0
∆ H f + C p dT
C, H2 , N2, O2
25C, 1atm
39
(c) Constructing inlet-outlet enthalpy table
(reference: C(s), H2(g), O2 (g), N2, @ 25C, 1atm)
• • ^
^
n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol
^
C3H8 100 H1 -- --
^ ^
O2 600 H2 100 H4
^ ^
N2 2256 H3 2256 H5 ^
CO2 -- -- 300 H6
^
H2O -- -- 400 H7

40
(d) Calculate the unknown specific enthalpy

3C(s) + 4H2 (g)  C3H8 (g) (@ 25C,1atm)

^  ^0 T0 T0=25C
H 1 =  ∆ H f 
  C3 H 8 ( g )
+ ∫
25
C P dT = −103.8 kJ / mol

^
H 2 = 8.74 kJ / mol O2 @ 300C relative to 25C, Table
B.8, no heat of formation

^ ^
H 3 H 5 Similar procedures above
41
^
H6 ^ 0
∆H f
C ( s,25C ,1atm) + O2 ( g ) 
→ CO2 ( g ,25C ,1atm)
^ ^ 0 1000
H6 = ∆H f +∫ C p ,CO2 dT = −344.9 kJ / mol
25
Table B.1 Table B.8
-393.5 KJ/mol 48.6 KJ/mol
^
H7 ^ 0
∆H f
H 2 ( g ,25C ,1atm) + 1 / 2O2 ( g ) 
→ H 2O(v,25C ,1atm)

^ ^ 0 1000
H7 = ∆H f +∫ C p , H 2O dT = −204.1 kJ / mol
25

42
 •
(e) calculate ∆ H for reactor
• • ^ • ^
∆ H = ∑ n out H out − ∑ n in H in

Note: the heat of reaction term is not required if

elements are chosen as references
(heat of reaction is implicitly included when heat of
formation of the reactants are subtracted from
those of products) •
∆ H = −1.26 ×105 kJ / s
(f) Overall energy balance
• • • • •
Q+ W s = ∆ H + ∆ E K + ∆ E P
43
(1) Process path for heat of reaction method

Inlet , Tin ∆H
•
Oulet , Tout
→
Re ac tan ts products
↑ ↑
reac tan ts ^ 0
∆Hr
products
o

→ o
25 C Table B.1
25 C

• • ^ 0 • ^ • ^
∆ H = ξ ∆ H r + ∑ n out H out − ∑ n in H in

Comment: must consider the extent of reaction !

44
(2) Process path for heat of formation method

Re ac tan ts ∆H
•
products
→
Tin Tout
^ 0
^ 0
∆ H f + C p dT Elementals ∆ H f + C p dT

25o C

• • ^ • ^
∆ H = ∑ n out H out − ∑ n in H in

Comment: No need to consider the extent of reaction 45

 Example: an ammonia oxidizer (P = 1atm)
Ex 9.5-1 @P453

4 NH 3 ( g ) + 5O2 ( g ) → 4 NO ( g ) + 6 H 2O(v)
^ 0
∆ H r = −904.7 kJ / mol

100 mol NO/s

100 mol NH3 /s
150 mol H2O/s
200 mol O2/s, 25C
75 mol O2/s, 300C
•
Q kJ / s
?????

46
Solution:
^ 0
is given, method 1 (heat of reaction) is
∆Hr
used

5 Steps

(a) Flow chart and material balance: done

(b) Reference state: 25C,1atm, NH3, O2, NO(g),
H2O(v)

47
(c) construct lnlet-outlet enthalpy table
Reference state: 25C,1atm, NH3(g), O2,
NO(g), H2O(v)
• ^ • ^
n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol

NH3 100 0 -- --
^
O2 200 0 75 H1
^
NO -- -- 100 H2
^
H2 O -- -- 150
H3

48
(d) calculate enthalpies:

O2 (g, 300C): ^
H 1 = 8.47 kJ / mol
(TableB.8)

NO (g, 300C):
^ 300
H2 = ∫ C P , NO dT
25

 
→ 8.453 kJ / mol
TableB .2

^
H2O (v, 300C): ∆ H 3 = 9.57 kJ / mol
(Table B.8) 49
 • •
(e) Calculate ξ , ∆ H

if 100mol/s of NH3 is consumed:

•
• n NH 3,r 100
ξ= = = 25 mol / s
ν NH 3
4
• • ^ 0 • ^ • ^
∆ H = ξ ∆ H r + ∑ n out H out − ∑ n in H in
= −19,700 kJ / s

50
(f) Overall energy balance:

• • • • •
Q+ W s = ∆ H + ∆ E K + ∆ E P
• •
Q ≈ ∆ H = −19,700 kW

51
Example : Energy Balance in a methane oxidizer (P
= 1atm), method (2) Ex 9.5-2 @P454

Reaction(1) CH4 (g) + O2  HCHO (g) + H2O(v)

Reaction(2) CH4 (g) + 2O2  CO2 (g) + 2H2O(v)

Continuous reactor 60 mol/s CH4

100 mol/s CH4 30 mol/s HCHO
25C 10 mol/s CO2
50 mol/s H2O (v)
100 mol/s O2 50 mol/s O2
376 mol/s N2, 100C •
376 mol/s N2 150C
Q kJ / s ?

52
Solution:
Multiple reactions with unknown heat of
reaction, method 2 has to be used.

Basis: 100 mol/s CH4 feed

(a) material balance, done,

(b) reference state: atomic species at 25C, 1 atm

 heat of formation method

53
Process path for heat of formation method

Re ac tan ts ∆H
•
products
→
Tin Tout

^ 0 Elements ^ 0
H f + C p dT
H f + C p dT
25C

54
(c) Construct inlet-outlet enthalpy table

Reference: C(s), O2(g), H2(g), N2(g) @ 25C, 1atm

• • ^
^
n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol
^ ^
CH4 100 H1 60 H4
^ ^
O2 100 H2 50 H5
^ ^
N2 376 H3 376 H6
^
HCHO -- -- 30 H7
^
CO2 -- -- 10 H8
^
H2O -- -- 50 H9

55
(d) calculate enthalpies
^ ^ 0
– CH4 (25C) : H 1 = (∆ H f ) CH 4 = −74.85 kJ / mol B.1
^ ^
– O2 (100C) : H 2 = H O2 (100C ) = 2.235 kJ / mol B.8
^ ^
– N2 (100C) : H 3 = H N 2 (100C ) = 2.178 kJ / mol B.8
^ ^ 0 150
– CH4 (150C): H 4 = (∆ H f ) CH 4 + ∫ C P ,CH 4 dT B.1, 2
25

= −69.65 kJ / mol
^ ^
– O2 (150C) : H 5 = H O2 (150C ) = 3.758 kJ / mol B.8
^ ^
– N2 (150C) : H 6 = H N 2 (150C ) = 3.655 kJ / mol B.8
^ ^ 0 150
– CH2O (150C): H 7 = (∆ H f ) HCHO + ∫ C P , HCHO dT B.1, 2
25

= −111.15 kJ / mol
^ ^ 0 ^
– CO2 (150C): H 8 = (∆ H f ) CO2 + H CO2 = −388.6 kJ / mol B.1,8
56
 ^ ^ 0 ^
-H2O (v, 150C): H 9 = (∆ H f ) H 2O ( v ) + H H 2O ( v ) (150C )
= − 237.56 kJ / mol

(e) Evaluate ΔH
• ^ • ^
∆H = ∑ n out H out − ∑ n in H in = −15,300 kJ / s

No need to evaluate reaction extents, ξ1

& ξ2, in this method

(f) Overall energy balance

Q = ∆H = −15,300 kJ / s

57
9.5b Unknown outlet conditions: adiabatic reactor

• Two types of processes:

– (1) inlet & outlet conditions specified,
determine heat input/output

– (2) Inlet condition and heat input/output

specified, determine outlet conditions
(1. energy; 2. mass)

• In an adiabatic reactor, outlet T needs to be

solved. 58
Example: An adiabatic reactor, energy balance
C2H5OH(v)  CH3CHO(v) + H2 (g)

100 mol 70 mol C2H5OH(v)

C2H5OH(v) reactor 30 mol C2H3OH (v)
400 C 30 mol H2, Tad ºC ??

Q=0
Solution:
(a) material balance, done on flow chart
(b) reference state: C2H5OH(v), CH3CHO(v),
H2(g) @ 25C, 1atm
59
(c) construct the inlet-outlet enthalpy table

reference state: C2H5OH(v), CH3CHO(v), H2(g)

@ 25C, 1atm

• ^ • ^
n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol
^ ^
C2H5OH 100 H1 70 H2
^
CH3CHO -- -- 30 H3
^
H2 -- -- 30 H4

(d) overall energy balance, for adiabatic reactor:

^ 0 ^ ^
∆H = ξ∆ H r + ∑ n out H out − ∑ n in H in = 0
60
 – Calculate the extent of reaction

(nCH 3CHO ) out − (nCH 3CHO )in 30 − 0

ξ= = = 30.0 mol
ν CH CHO 3
1
– Calculate standard heat of reaction

^ 0 ^ 0 ^ 0
∆Hr = ∑ν ∆ H
products
i fi − ∑ν ∆ H
reac tan ts
i fi = 69.11 kJ / mol

(e) Calculate the enthalpies

^ 400
Inlet H1 = ∫C
25
P ,C 2 H 5OH dT = 33.79 kJ / mol

61
 Tad CH3CHO, C2H5OH, H2
^
Outlet: H i = ∫ C P ,i dT
@ outlet temperature, Tad
25

C P = a + bT + cT + dT +  ,
2 3 (Table B.2)

(f) solve energy balance for Tad

^ 0 ^ ^
∆H = ξ∆ H r + ∑ n out H out − ∑ n in H in = 0
^ 0 ^ ^ ^ ^
= 30 × ∆ H r + 70 × H 2 + 30 × H 3 + 30 × H 4 − 100 × H 1

This is a polynomial equation in terms

of Tad, solve it, Tad = 185 C
62
 For the process in which inlet condition and heat
input/output are specified, to determine outlet conditions
( mass)
• Simultaneous material & energy balance
C2H5OH(v)  CH3CHO(v) + H2 (g)

150 mol/s, 300C 253C

•
90 mol% C2H5OH(v) n1 mol C2H5OH(v)/s
•
10 mol% CH3CHO(v) n 2 mol C2H3OH (v)/s
•
n 3 mol H2/s
2440 kW

Calculate: fractional conversion of

ethanol in the reactor
63
Solution:
(a)Degree of freedom analysis:
Unknown = 3,
Equation = 3
( 1 energy balance, 1 C , 1 H)
(b) Material balance:
• •
For C n1 + n 2 = 150 mol / s Eq(1)
• • •
For H 150 × 0.9 × 6 + 150 × 0.1× 4 = 6 n1 + 4 n 2 + 2 n 3
• • •
3 n1 + 2 n 2 + n 3 = 435 mol ( H ) / s Eq(2)
64
(c) Reference state:
elemental species C(s), H2(g), O2(g) @ 25C,1atm
(heat of formation method)
(d) energy balance

To calculate specific enthalpy of each species,

using:
^ ^ 0 T Inlet: T = 300C
H i = ∆ H fi + ∫ CP ,i (T ) dT Outlet: T = 253C
25
Standard enthalpy of formation
(Table B.1)

• • • ^ • ^
Q = ∆ H = ∑ n out H out − ∑ n in H in
65
(e) construct inlet-outlet enthalpy table

Reference state:
C(s), H2(g), O2 (g) @ 25C, 1atm

• •
^ ^
species n in H in n out H out
Mol/s kJ/mol mol/s kJ/mol
•
C2H5OH 135 -212.19 n1 -216.81
•
CH3CHO 15 -147.07 n2 -150.90
•
H2 -- -- n3 6.595

66
(f) using the overall energy balance:
• • • ^ • ^
Q = ∆ H = ∑ n out H out − ∑ n in H in = 2440 kJ / s

• • •
28,412 kJ / s = 216.81 n1 + 150.90 n 2 − 6.595 n 3 Eq(3)

Solving eq. (1), eq(2) and eq(3) :

•
n1 = 92.0 mol C2 H 5OH / s
•
n 2 = 58.0 mol CH 3CHO / s
•
n 3 = 43.0 mol H 2 / s

67
Fractional conversion of ethanol:

• •
(n C2 H 5OH ) in − (n C2 H 5OH ) out 135 − 92
x= •
=
(n C2 H 5OH ) in 135
= 0.319

68