CHAPTER 5-ENERGY BALANCE

FOR REACTIVE SYSTEM

CHE243-MATERIAL AND ENERGY BALANCE AND
SIMULATION

HEAT OF
REACTION

HESSS LAW

HEAT OF
FORMATION

HEAT OF
COMBUSTION

HEAT OF REACTION
Heat of reaction (or enthalpy of reaction) Hr (T,P) is the enthalpy
change for a process in which stoichiometric quantities of reactants at
temperature T and pressure P react completely in a single reaction to form
products at the same temperature and pressure. Refer Felder pp. 442
Stoichiometric quantities of reactions molar amounts of the
reactants numerically equal to their stoichiometric coefficients.
Consider the reaction between solid calcium carbide and liquid water
to form solid calcium hydroxide and gaseous acetylene:

CaC 2 s 2H 2Ol

CaOH 2 s C 2 H 2 g

The heat of the calcium carbide reaction at 25 0C and 1 atm is:

H product H reactant Hr 125.4

kJ
mol

HEAT OF REACTION

Several important terms and observations related to heats of reactions:

If Hr (T,P) is negative, the reaction is exothermic
If Hr (T,P) is positive, the reaction is endothermic

At low and moderate pressures, Hr (T,P) is nearly independent of pressure.

The value of heat of reaction depends on how the stoichiometric equation is
written. Refer Felder pp. 443
The value of a heat of reaction depends on the state of aggregation (gas,
liquid, or solid) of the reactants and products.
The standard heat of reaction, H0r is the heat of reaction when both
the reactants and products are at specified reference temperature
and pressure, usually 25 0C and 1 atm.

HESSS LAW

Hesss Law If the stoichiometric equation for reaction 1 can be obtained by

algebraic equations (multiplication by constants, addition, and subtraction)
on stoichiometric equations for reaction 2, 3, then the heat of reaction H0r1
can be obtained by performing the same operations on the heats of reactions
H0r2, H0r3. Refer Felder pp. 446

Example Hesss Law (Felder pp 446)

The standard heats of the following combustion reactions have been
determined experimentally:
. CH +
1.
2 6

3.5O2

2. C +

O2

3. H2 +

0.5O2

2CO2 +

CO2

H2O

3H2O

H0r1 = -1559.8 kJ/mol

H0r2 = -393.5 kJ/mol
H0r3 = -285.8 kJ/mol

Use Hesss law and the given heats of reaction to

determine the standard heat of reaction:
4. 2C +

3 H2 C2H6

^ 0

kJ
H r4 84.6
mol

H0r4 = ???

HEAT OF FORMATION

A formation reaction a compound is formed from its elemental

constituents as they normally occur in nature. Refer Felder pp. 447
Standard heat of formation, H0f the enthalpy change associated
with the formation of 1 mole of the compound at a reference
temperature and pressure (usually 25 0C and 1 atm)
The H0f for elemental species (eg. O2, N2, C, etc..) is zero (0).
The standard heat of reaction, H0r is:
^ 0

^ 0

H r vi H fi
i

^ 0

v H
i

products

fi

^ 0

v H
i

reactan ts

fi

Example Determination heat of reaction from heats of formation

(Felder pp 447)
.Determine the standard heat of reaction for the combustion of liquid npentane, assuming H2O (l) is a combustion product

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

^ 0

H r 3509.54

kJ
mol

HEAT OF COMBUSTION

Standard heat of combustion, H0c the heat of combustion of that

substance with oxygen to yield a specified products, with both
reactants and products at 25 0C and 1 atm. Refer Felder pp. 448
The standard heat of reaction, H0r that involve only combustible
substances and combustion products that can be calculated from
tabulated standard heats of combustion.

^ 0

^ 0

H r vi H c i
i

^ 0

v H
i

reactan ts

ci

^ 0

v H
i

products

ci

Example Determination heat of reaction from heats of combustion

(Felder pp 449)
.Determine the standard heat of reaction for the dehydrogenation of
ethane:

C2H6 C2H4 + H2

^ 0

kJ
H r 136.93
mol

PROCEDURE CALCULATION

SIMPLE ENERGY BALANCE

CALCULATION

HEAT OF
REACTION
METHOD

HEAT OF
FORMATION
METHOD

HEAT OF REACTION METHOD

100 mol C3H8 (g)/s

T=250C

600 mol O2 (g)/s

2256 mol N2 (g)/s
T=3000C

100 mol O2 (g)/s

2256 mol N2 (g)/s

Q (kJ/s)

300 mol CO2 (g)/s

400 mol H2O (g)/s
T=10000C

For single reaction where H0r is known. Refer Felder pp. 450
Complete the material balance calculations on the reactor to the greatest
extent possible.
Choose reference states for specific enthalpies calculation the best choice is
25 0C and 1 atm.

For a single reaction in a continuous process, calculate the extent of reaction,

Prepare inlet outlet enthalpy table.

References: C3H8 (g), O2 (g), N2 (g), CO2 (g), H2 O (l), at 250C, 1 atm

Substances

min
( mol/s)

Hin
(kJ/mol)

mout
( mol/s)

Hout
(kJ/mol)

C3H8

100

O2

600

H2

100

H4

N2

2256

H3

2256

H5

CO2

300

H6

H2O

400

H7

Calculate the unknown stream component enthalpy

H 2 H for O2 (250 C 3000 C)

From Table B.8, H2 8.47

kJ
mol

Calculate H for the reactor. Use one of the following formula:

.

^ 0

H H r n H n H
out
.

in

^ 0

H
j

reaction

(for single reaction)

rj

n H n H
out

From energy balance, calculate Q

in

(for multiple reaction)

HEAT OF FORMATION METHOD

100 mol C3H8 (g)/s
T=250C

600 mol O2 (g)/s

2256 mol N2 (g)/s
T=3000C

100 mol O2 (g)/s

2256 mol N2 (g)/s

Q (kJ/s)

300 mol CO2 (g)/s

400 mol H2O (g)/s
T=10000C

Preferably for multiple reactions and single reactions where H0r is not
available. Refer Felder pp. 451
Complete the material balance calculations on the reactor to the greatest
extent possible.
Choose reference states for specific enthalpies calculation the best
choice is 25 0C and 1 atm.

Prepare inlet outlet enthalpy table.

References: C3H8 (g), O2 (g), N2 (g), CO2 (g), H2 O (l), at 250C, 1 atm

Substances

nin
( mol/s)

Hin
(kJ/mol)

nout
( mol/s)

Hout
(kJ/mol)

C3H8

100

H1

O2

600

H2

100

H4

N2

2256

H3

2256

H5

CO2

300

H6

H2O

400

H7

Calculate the unknown stream component enthalpy

H 1 H for C 2 H 8 (at 250 C)

T

H 1 H 0f Cp(T)dT
25

25

kJ
H 1 103.8 Cp(T)dT 103.8
mol
25
Calculate H for the reactor. Use one of the following formula:
.

H n H n H
out

From energy balance, calculate Q

in

Example Energy Balance About an Ammonia Oxidizer (Felder pp 453)

The standard heat of reaction for the oxidation of ammonia is given

below:
0
. 4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O(v) : H r=-904.7 kJ/mol
100 mol NH3 /s and 200 mol O2 /s at 25 0C are fed into a reactor in which
the ammonia is completely consumed. The product gas emerges at
300 0C. Calculate the rate at which heat must be transferred to or from
the reactor, assuming operation at approximately 1 atm.

Q 19,701.45kW

Example Energy Balance About a Methane Oxidizer (Felder pp 454)

Methane is oxidized with air to produce formaldehyde in a continuous
reactor. A competing reaction is the combustion of methane to form CO2
.1. CH4 (g) + O2 (g) HCHO (g) + H2O(v)
2. CH4 (g) + 2O2 (g) CO2 (g) + 2H2O(v)

A flow chart of the process for an assumed basis of 100 mol methane
fed to the reactor is shown in Figure 1. Calculate the rate at which heat
must be transferred to or from the reactor, assuming operation at
approximately 1 atm.

Q 15,382 kJ

Example Simultaneous Material and Energy Balance (Felder pp 458)

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)
The fractional conversion of ethanol:

n feed n unreacted
0.313
n feed