Calculation of Enthalpy Changes

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 Btu0 F
lbmol
K
1
 14.1 Heat Capacity Equations

Heat Capacities of Ideal Gases

Type of Molecule High Temperature Low

Temperature
Monoatomic
5R/2 5R/2
Polyatomic, linear
(3n – 3/2)R 7R/2
Polyatomic, nonlinear (3n – 2)R 4R

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

2
 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
C P 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 =  + T + T2

where , , and  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 14–1. 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 9.2%
CO 1.5%
O2 7.3%
N2 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 14–1. Calculation of H for a Gas Mixture

The heat capacity equations for the gases are:

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

N2: CP = 6.895 + 0.7624 × 10-3T – 0.7009 × 10-7T2

O2: CP = 7.104 + 0.7851 × 10-3T – 0.5528 × 10-7T2

CO: CP = 6.865 + 0.8024 × 10-3T – 0.7367 × 10-7T2

CO2: CP = 8.448 + 5.757 × 10-3T – 21.59 × 10-7T2

+ 3.059 × 10-10T3

5
 Example 14–1. 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
C P avg   xi CPi
i 1
 xO2CP xCO2CP  xCOCP
C P avg  x N 2 C P
N2
O2 CO 2 CO

6
 Example 14–1. Calculation of H for a Gas Mixture

x N2 C PN2 0.826.895 ....

x O2 C P O2
0.0737.104 ....
x CO2 C P CO
2
0.0928.448 ....
x CO C P CO 0.0156.865 ....
Obtaining xiCPi:
CP avg  7.053  1.2242  10 T  2.6124
 10 3
T
7
2

 0.2814 1010 T3
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 Example 14–1. Calculation of H for a Gas Mixture

Solving for H:

200  7.053 1.2242 103 T  2.6124 107 T2

H    0.2814  10 10 3
T 
dT

550 
1.2242 103
H  7.053200  550 2 2002  5502
 0.2814  10 10
 5504
2.6124 10 7 3 3 4
 3 200  550   4 20
H  2616 Btu /  0 
lbmol

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 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 Enthalpies of Combustion Gases
D.6
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 14.3 Enthalpy Calculations from Standard Heat of Formation

The enthalpy from a standard reference state is given by

T
H  Hf   CP dT
TR

where Hfo is the standard heat of formation and T R is the

reference temperature.
For a mixture,


N T
CP dT
Hmixture  
i 1H f  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

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 14.3 Enthalpy Calculations from Standard Heat of Formation

Consider an open system with no chemical reaction:

Input, T1 Open System Output, T2

A: HA1 (No A: HA2
B: Reaction) B:
HB1 HB2

The enthalpy difference between inlet and outlet will be

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

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 14.3 Enthalpy Calculations from Standard Heat of Formation

Calculating the enthalpies from standard heat of

formation

 
H  H fA   T C PA
TR
2
fB
dT  H  
T


TR C PB
2





 T
dT
 fA TR C PA
H 
1
fB

dT  H  
T
TR C PB
1

dT

 
Simplifying,

H   T C PA dT   T C PB dT
2 2
T1 T1

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 14.3 Enthalpy Calculations from Standard Heat of Formation

Consider an open system with chemical reaction:

Input, T1 Open System Output, T2

A: HA A+B ===> C+D C: HC
B: D: HD
HB

The enthalpy difference between inlet and outlet will be

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

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 14.3 Enthalpy Calculations from Standard Heat of Formation

Calculating the enthalpies from standard heat of

 
formation
 
H  H fC   C PC
T T

 
2 2
TR fD TR C PD
dT  H  

 
H fA   T CdT
TR PA
1
fB
dT  H   
T
TR C PB


1

Rearranging the terms,
dT

H  H  H   H 
fC fD

fA  fB dT T2
TR C PC

 HT C PD dT   T C PA dT
2
  1T
C PB dT 1
T R T T
R R

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 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 products  i nHf 
reactants i

The n in the equation is the stoichiometric

in the chemical reaction.  nH f  
coefficient of species i

The standard heat of reaction is the difference between the heats

of formation of the products and that of the reactants.

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 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 NO = +90.374 kJ/mol
O2: 0 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

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