ENERGY BALANCE

FOR REACTIVE
SYSTEM:
PART 3

Credit to:
CHE531 CPPII DR SITI WAHIDA & PM Dr JUN
 LECTURE OUTLINE

01 HEATS OF
REACTION GENERAL PROCEDURES
04 OF RXTIVE EB
• ADIABATIC
REACTORS

02 HEATS OF
FORMATION

05 THERMOCHEMISTRY

03 HEATS OF OF SOLUTIONS

COMBUSTION

CHE531 CPPII
ADIABATIC REACTORS
 ADIABATIC REACTOR
Q = ∆H = 0

✭ The input conditions, heat input and product composition are specified
✭ Need to determine the unknown T or amount of reactant/product
✭ Heat for reaction method or heat of formation method equations can
be used to detemine the unknown

Go thru’ :
Example 9.5-3

Example 9.5-4

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CHE531 CPPII
EXAMPLE: Simultaneous Material and Energy Balance

The ethanol (C2H5 OH) dehydrogenation reaction is to be carried out with the feed entering at
3000C. The feed contains 90.0 mol% ethanol and the balance acetaldehyde and enters the reactor
at a rate of 150 mol/s. To keep the temperature from dropping too much and thereby decreasing
the reaction rate to an unacceptably low level, heat is transferred to the reactor. When the heat
addition rate is 2440 kW, the outlet temperature is 2530C. Calculate the fractional conversion of
ethanol achieved in the reactor. The reaction of dehydrogenation of ethanol to form acetaldehyde
is stated as:
C2H5 OH (v) → CH3 CHO (v) + H2(g)
SOLUTION:
Take basis of calculation: 150 mol/s feed gas
Flow chart of process: 150 mol/s n1 mol C2H5OH/s
0.9 mol C2H5OH (v)/mol n2 mol CH3CHO /s
0.1 mol CH3CHO (v)/mol n3 mol H2/s
T=3000C T=2530C

2440 kW

• We cannot simply do material balance – information is not enough

Reference state for all component is vapor/gas at 25 0C and 1 atm
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CHE531 CPPII
Cont…EXAMPLE:
Simultaneous MEB

150 mol/s n1 mol C2H5OH/s • Calculate the unknown stream component enthalpy
0.9 mol C2H5OH (v)/mol n2 mol CH3CHO /s
0.1 mol CH3CHO (v)/mol n3 mol H2/s Use Table B.2 to calculate H forC 2 H 5OH and CH 3CHO
T=3000C T=2530C
300
kJ
2440 kW ( 0
)
For C 2 H 5OH T = 300 C , H1 = ΔH + ò Cp(T)dT = -235.31 + 23.15 = -212.16
0
f
mol
25
• Prepare inlet – outlet enthalpy table. 253
kJ
References: C2H5OH (v), CH3CHO (v), H2 (g), at 250C, 1 atm (T = 253 C ), H
0
3 = ΔH 0f + ò Cp(T)dT = -235.31 + 18.52 = -216.79
mol
25

Substances nin Hin nout Hout 300

kJ
( mol/s) (kJ/mol) ( mol/s) (kJ/mol)
( 0
)
For CH 3CHO T = 300 C , H 2 = ΔH + ò Cp(T)dT = -166.2 + 19.13 = -147.07
0
f
mol
25
253
kJ
C2H5OH 135 H1 n1 H3
(T = 253 C ), H
0
4 = ΔH 0f + ò Cp(T)dT = -166.2 + 15.30 = -150.9
mol
25

Use Table B.8 to calculate H for component H 2

CH3CHO 15 H2 n2 H4
253
kJ
( 0
)
For H 2 T = 253 C , H 5 = ΔH + 0
f ò Cp(T)dT = 0 + 6.597 = 6.597 mol
H2 - - n3 H5 25

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CHE531 CPPII
Cont…EXAMPLE: 150 mol/s n1 mol C2H5OH/s
0.9 mol C2H5OH (v)/mol n2 mol CH3CHO /s
Simultaneous MEB 0.1 mol CH3CHO (v)/mol
T=3000C
n3 mol H2/s
T=2530C

2440 kW

References: C2H5OH (v), CH3CHO (v), H2 (g), at 250C, 1 atm

(- 216.79n1 - 150.9n2 + 6.597n3 )out - (- 212.6(135 ) - 147.07(15 ))in = 2440 kJ
Substances nin Hin nout Hout
s
( mol/s) (kJ/mol) ( mol/s) (kJ/mol) - 216.79n1 - 150.9n2 + 6.597n3 + 30,907 = 2440
C2H5OH 135 -212.6 n1 -216.79 - 216.79n1 - 150.9n2 + 6.597n3 = -28,467 ® Equation (1)
CH3CHO 15 -147.07 n2 -150.9 • Analyze atomic balance on each atom involved:
H2 - - n3 6.597 C = 2 unknown (n1, n2)
H = 3 unknown (n1, n2, n3)
O = 2 unknown (n1, n2)
• From energy balance:
.
• Do atomic balance on C
For open system, Q = Δ H
135(2) + 15(2) = 2n1 + 2n2
^ ^ kJ
å nΔ H - å nΔ H = 2440
s
n1 + n2 = 150
Eq (2)
out in
n1 = 150 - n2 ®
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CHE531 CPPII
Cont…EXAMPLE: 150 mol/s n1 mol C2H5OH/s
0.9 mol C2H5OH (v)/mol n2 mol CH3CHO /s
Simultaneous MEB 0.1 mol CH3CHO (v)/mol
T=3000C
n3 mol H2/s
T=2530C

2440 kW
• Atomic balance on O would give the same
- 216.79n1 - 150.9n2 + 6.597n3 = -28,467 ® Equation (1)
equation with C
216.79(150 - n2 ) + 150.9n2 - 6.597n3 = 28,467
• Atomic balance on H 32,518.5 - 216.79n2 + 150.9n2 - 6.597n3 = 28,467
- 65.89n2 - 6.597n3 = -4051.5
135(6 ) + 15(4 ) = 6n1 + 4n2 + 2n3
6n1 + 4n2 + 2n3 = 870 Insert Equation 3a into equation above
3n1 + 2n2 + n3 = 435 ® Eq (3) - 65.89n2 - 6.597(n2 - 15 ) = -4051.5
- 72.487n2 + 98.955 = -4051.5
• Insert Eq 2 into equation 1 and 3
72.487n2 = 4150.455
3n1 + 2n2 + n3 = 435 ® Eq (3) mol
n2 = 57.26
s
3(150 - n2 ) + 2n2 + n3 = 435
From Eq 3a, n3 = n2 - 15
450 - 3n2 + 2n2 + n3 = 435
n3 = 57.26 - 15
n3 = n2 - 15 ® Eq (3a )
mol
n3 = 42.26 8
s CHE531 CPPII
Cont…EXAMPLE: 150 mol/s n1 mol C2H5OH/s
Simultaneous MEB 0.9 mol C2H5OH (v)/mol
0.1 mol CH3CHO (v)/mol
n2 mol CH3CHO /s
n3 mol H2/s
T=3000C T=2530C

2440 kW

From Eq 2, n1 = 150 - n2
n1 = 150 - 57.26
mol
n1 = 92.74
s

• The fractional conversion of ethanol:

n feed - nunreacted 135 - 92.74

= = 0.313
n feed 135

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CHE531 CPPII
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CHE531 CPPII
 THERMOCHEMISTRY OF SOLUTIONS

Standard Heat of Formation of the solution: The enthalpy change

associated with the formation of a solution from the solute element and
solvent at 25 OC.
If a solution contains n moles of solvent per mole of solute, then:
æ ^o ö æ ^o ö ^ o→ Eqn. 9-5.3
çç D H f ÷÷ = çç D H f ÷÷ + D H s (n)
è ø solution è ø solute
^ o
where D Hs (n) is the heat solution at 25 OC

The dimension of Heat of formation and solution are (energy)/(mole of

solute).

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CHE531 CPPII
 THERMOCHEMISTRY OF SOLUTIONS
The standard heat of reaction involving solutions may be calculated from heat of formation of
the solutions.
For example, for the reaction:
2 HNO 3 (aq, r = 25) + Ca(OH )2 (aq, r = ¥ ) ® Ca(NO 3 )2 (aq, r = ¥ ) + 2H 2 O[l]

The standard heat of reaction is

^ o æ ^o ö æ ^o ö æ ^o ö æ ^o ö
D Hr = çç D H f ÷÷ + 2çç D H f ÷÷ - 2çç D H f ÷÷ - çç D H f ÷÷
è øCa ( NO3 )2 (aq ,r =¥ ) è ø H 2O (l ) è ø HNO3 (aq ,r = 25 ) è øCa (OH )2 (aq ,r =¥ )
^ o
D Hr = -114.2 kJ / mol

If the standard heat of formation is tabulated for a solution involved o

in the reaction, the
^
tabulated value may be substituted directly into the expression for D H ; otherwise æç D H^ of ö÷
r ç ÷
è ø solution
must be first calculated as in Eq. 9-5.3.

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CHE531 CPPII
 THERMOCHEMISTRY OF SOLUTIONS
Calculate DH for reactive process as :

DH = ån H - ån H
out
i i
in
i i

and for solution, specific enthalpy usually has the dimension of (energy) / (mole of solute).

To calculate the specific enthalpy of a solution at a temperature T in (energy)/(mole of solute):

** first calculate m, the mass of solution corresponding to 1 mole of dissolved solute, and then
T

ò (C )
add m to the standard heat of formation of the solution.
p solution
dT
25 o C

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CHE531 CPPII
 Example 9.5-5: Standard Heat of Neutralization reaction

^ o
1. Calculate the D Hr for the reaction:

H 3 PO 4 (aq, r = ¥ ) + 3NaOH(aq, r = 50 ) ® Na 3 (PO 4 )(aq, r = ¥ ) + 3H 2 O[l]

SOLUTION:

From Perry’s Chemical Engineers’ Handbook:

æ ^o ö
çç D H f ÷÷ = - 309.32 kcal / mol = - 1294 kJ / mol From Table B1 and B11
è ø H 3 PO4 (aq ,r =¥ )
æ ^o ö æ ^o ö ^ o
æ ^o ö NaOH (aq, r = 50 ) : çç D H f ÷÷ = çç D H f ÷÷ + D H s (r = 50 )
çç D H f ÷÷ = - 471.9 kcal / mol = - 1974 kJ / mol è ø NaOH (aq ) è ø NaOH ( s )
è ø Na3 PO4 (aq ,r =¥ )
(
= - 426.6 kJ/mol + - 42.51 kJ/mol
Table B1 Table B11
)
æ ^o ö
From Table B1 çç D H f ÷÷ = -469.11 kJ/mol
è ø NaOH (aq ,r = 50 )
æ ^o ö
çç D H f ÷÷ = - 285.8 kJ / mol
è ø H 2O (l )
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CHE531 CPPII
Cont…Example 9.5-5: Standard Heat of Neutralization reaction
^ o
Calculate D Hr
^ o æ ^o ö æ ^o ö æ ^o ö æ ^o ö
D Hr = çç D H f ÷÷ + 3çç D H f ÷÷ - çç D H f ÷÷ - 3çç D H f ÷÷
è ø Na3 PO4 (aq ,r =¥ ) è ø H 2O (l ) è ø H 3 PO4 (aq ,r =¥ ) è ø NaOH (aq ,r = 50 )
^ o
D Hr = -1974 + 3(- 285.8 ) - (- 1294 ) - 3(- 469.11)
^ o
D Hr = -130.1 kJ / mol

2. If 5.00 mol of NaOH dissolved in 250 ml of water is neutralized completely at 25 OC with dilute
phosphoric acid, what is the attendant enthalpy change?

SOLUTION:
-130.1 kJ
(
DH 25 o C = ) 3.00 mol NaOH
´ 5.00 mol NaOH = -217 kJ

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CHE531 CPPII
Example 9.5-6: E balance on a Neutralization process

A 10.0 wt% aqueous solution of H2SO4 at 40 OC is to be neutralized with a 20.0 wt%

aqueous solution of NaOH at 25 OC in a continuous reactor. At what rate in kJ/kg H2SO4
solution must heat be removed from the reactor if the product solution emerges at 35 OC?
H 2 SO 4 (aq, 10%) + 2NaOH(aq, 20%) ® Na 2 (SO 4 )(aq ) + 2H 2 O[l]
SOLUTION:

Basis of calculation: 1 kg of H2SO4 1000 g of H2SO4, 40 OC

0.10 g H2SO4 / g
0.90 g H2O / g
MIXER m2 (g) of Na2SO4
Solve material balance for this m3 (g) of H2O
process m1 (g) of NaOH, 25 OC 35 OC

Do atomic balance: 0.20 g NaOH / g

0.80 g H2O / g

Na : 2 unknowns (m1 , m2 )
S : 1 unknown (m2)
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CHE531 CPPII
Cont…Example 9.5-6: E balance on a Neutralization process

Do Atomic balance for S

1 mol S 1 mol S
32.0 g S 32.0 g S
100 g H 2SO 4 ´ = m2 ´
98.1 g H 2SO 4 142 g Na 2SO 4
1 mol H 2SO 4 1 mol Na 2SO 4

m2 = 145 g Na 2SO 4

Do Atomic balance for Na

1 mol Na 2 mol Na
23.0 g Na 2(23) g Na
0.2m1 g NaOH ´ = 145 g Na 2SO 4 ´
40.0 g NaOH 142 g Na 2SO 4
1 mol NaOH 1 mol Na 2SO 4

m1 = 408 g NaOH ( aq)

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CHE531 CPPII
Cont…Example 9.5-6: E balance on a Neutralization process

Calculate mass of water, m3

Mass in = Mass out

1000 g + 408 g = 145 g + m3
m3 = 1263 g H 2O (l)
Mass of product solution, m = m2 + m3 = 145 + 408 = 553 g
1 mol 2 mol H 2O
Water formed by reaction = 145 g Na 2SO 4 formed ´ ´
142 g 1 mol Na 2SO 4
= 2.04 mol H 2O

Calculate solvent / solute mole ratios…….Refer text book

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CHE531 CPPII
EQ 2016 - QUESTION 5

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CHE531 CPPII
THE END OF TOPIC 3: PART 3