14

Calculation of Enthalpy Changes

hg

Manolito E. Bambase Jr
Assistant Professor, Department of Chemical Engineering
CEAT, University of the Philippines, Los Banos, Laguna, Philippines

14.1 Heat Capacity Equations

As shown previously, the change in enthalpy can be calculated

using the heat capacity CP.

H CP dT
To give the heat capacity some physical meaning, CP represents
the amount of energy required to increase the temperature of a
given amount of substance by 1 degree.
Common units for CP:

kJ
kmol K

Btu
lbmol 0 F
1

14.1 Heat Capacity Equations

Heat Capacities of Ideal Gases

Type of Molecule
Monoatomic
Polyatomic, linear
Polyatomic, nonlinear

High Temperature

Low Temperature

5R/2

5R/2

(3n 3/2)R

7R/2

(3n 2)R

4R

n = number of atoms per molecule ; R = ideal gas constant ; CV = CP R

14.1 Heat Capacity Equations

For gas mixtures, the CP of the mixture is the mole weighted

average of the heat capacities of the components:
N

CP avg xi CPi
i 1

If CP is not constant for the given temperature range, it may be

expressed as a function of temperature in a power series such as:
CP = a + bT + gT2
where a, b, and g are constants specific to a particular substance
(Appendix E.1, Basic Principles and Calculations in Chemical
Engineering, 6th edition, by David M. Himmelblau)
3

Example 141. Calculation of H for a Gas Mixture

An economic feasibility study indicates that solid municipal

waste can be burned to a gas of the following composition (on a
dry basis):
CO2
CO
O2
N2

9.2%
1.5%
7.3%
82.0%

What is the enthalpy difference for this gas per lbmol between
the bottom and the top of the stack if the temperature at the
bottom of the stack is 5500F and the temperature at the top is
2000F.
4

Example 141. Calculation of H for a Gas Mixture

The heat capacity equations for the gases are:

[T in 0F; CP in Btu/(lbmol)(0F)]

N2:
O2:
CO:
CO2:

CP = 6.895 + 0.7624 10-3T 0.7009 10-7T2

-3

-7 2

-3

-7 2

CP = 7.104 + 0.7851 10 T 0.5528 10 T

CP = 6.865 + 0.8024 10 T 0.7367 10 T
-3

-7 2

CP = 8.448 + 5.757 10 T 21.59 10 T

+ 3.059 10-10T3

Example 141. Calculation of H for a Gas Mixture

Basis: 1.00 lbmol of gas mixture

The enthalpy difference (H) is calculated as:

H CP dT
The CP of the gas mixture is determined from the equation:
N

CP avg xi CPi
i 1

CP avg x N2CP

N2

x O2 CPO 2 x CO2 CPCO 2 x CO CPCO

Example 141. Calculation of H for a Gas Mixture

x N2 CPN 2 0.82 6.895 ....

x O2 CPO 2 0.073 7.104 ....
x CO2 CPCO 2 0.092 8.448 ....
x CO CPCO 0.015 6.865 ....
Obtaining SxiCPi:

CP avg 7.053 1.2242 10

0.2814 10
7

T 2.6124 10 T

10

Example 141. Calculation of H for a Gas Mixture

Solving for H:
H

200 7.053 1.2242 10

550

T 2.6124 107 T 2
dT
10 3
0.2814 10 T

1.2242 103
H 7.053 200 550
2002 5502
2
10
2.6124 107
0.2814

10

2003 5503
2004 5504
3
4
H 2616 Btu / lbmol

14.2 Tables of Enthalpy Values

Enthalpies at various temperatures can also be obtained from tables.

From Basic Principles and Calculations in Chemical Engineering by
David M. Himmelblau (6th edition):

Table D.2

Enthalpies of Paraffinic Hydrocarbons (C1 C6)

Table D.3

Enthalpies of Other Hydrocarbons (ethylene,

propylene, butene, acetylene, benzene)

Table D.4

Enthalpies of Nitrogen and Some of its Oxides

Table D.5

Enthalpies of Sulfur Compounds

Table D.6

Enthalpies of Combustion Gases

9

14.3 Enthalpy Calculations from Standard Heat of Formation

The enthalpy from a standard reference state is given by

T

H H f CP dT
TR

where Hfo is the standard heat of formation and TR is the

reference temperature.
For a mixture,
N

H mixture H f CP dT
i 1

TR

10

14.3 Enthalpy Calculations from Standard Heat of Formation

The standard heat of formation (Hfo) is the special enthalpy for

the formation of 1 mole of a compound from its constituents
elements, for example
C(s) + 0.5O2(g) ======> CO(g)
The reactants and products must be at 250C and 1 atm.
The reaction may not represent a real reaction. By definition, the
heat of formation for the elements is zero in the standard state.
From Basic Principles and Calculations in Chemical Engineering by
David M. Himmelblau (6th edition):

Table F.1

Heats of Formation and Combustion

11

14.3 Enthalpy Calculations from Standard Heat of Formation

Consider an open system with no chemical reaction:

Input, T1
A: HA1
B: HB1

Open System
(No Reaction)

Output, T2
A: HA2
B: HB2

The enthalpy difference between inlet and outlet will be

H = Hout Hin = (HA2 + HB2) (HA1 + HB1)

12

14.3 Enthalpy Calculations from Standard Heat of Formation

Calculating the enthalpies from standard heat of formation

T2
T2

H H fA CPA dT H fB CPB dT

TR
TR
T1
T1

H fA CPA dT H fB CPB dT

TR
TR

Simplifying,
T2

T2

T1

T1

H CPA dT CPB dT

13

14.3 Enthalpy Calculations from Standard Heat of Formation

Consider an open system with chemical reaction:

Input, T1
A: HA
B: HB

Open System
A+B ===> C+D

Output, T2
C: HC
D: HD

The enthalpy difference between inlet and outlet will be

H = Hout Hin = (HC + HD) (HA + HB)

14

14.3 Enthalpy Calculations from Standard Heat of Formation

Calculating the enthalpies from standard heat of formation

T2
T2

H H fC CPC dT H fD CPD dT

TR
TR
T1
T1

H fA CPA dT H fB CPB dT

TR
TR

Rearranging the terms,

H H fC H fD H fA H fB CPC dT

TR
T2

T2

T1

T1

TR

TR

TR

CPD dT CPA dT CPB dT

15

14.3 Enthalpy Calculations from Standard Heat of Formation

The group of terms involving the standard heats of formation is

called the standard heat of reaction, HoR.
In general,

H R

nHf
products

nHf
reactants

The n in the equation is the stoichiometric coefficient of species i

in the chemical reaction.
The standard heat of reaction is the difference between the heats
of formation of the products and that of the reactants.
16

Example 14-2. Calculation of Standard Heat of Reaction

Calculate HRo for the following reaction:

4 NH3(g) + 5 O2(g) =====> 4 NO(g) + 6 H2O(g)
The standard heats of formation of the products and reactants are:
NH3: 46.191 kJ/mol
O2: 0

NO = +90.374 kJ/mol
H2O = 241.826 kJ/mol

And the standard heat of reaction:

HRo = [4(90.374) + 6( 241.826)] [4( 46.191) + 5(0)]
HRo = 904.696 kJ/4 mol NH3
17