Chemical Engineering

Thermodynamics

Chapter 2
Heat Effects
 Chapter Outline
2.3 Standard Heat of Reaction,
Formation and Combustion

2.4 Temperature Dependence of

Delta H
2.3 Standard Heat of Reaction,
Formation and Combustion
We have discussed the heat
effects for physical processes.
Chemical processes also
accompanied by transfer of
heat and temperature changes.
Most of heat effects for chemical reactions
are calculated in standard way.
The heat of specific reaction depends on
temperature of both reactants and products.
 Standard Heat of Reaction
Enthalpy change of reaction is called the
heat of reaction.
Q  H
Given the reaction:
aA  bB  lL  mM
The standard heat of reaction is defined as
the enthalpy change when a moles of A and
b moles of B react to form l moles of L and m
moles of M in their standard states at temp. T.
What is standard state?
A standard state is a particular state of a
species at temperature T and at specified
conditions of pressure, composition and
physical conditions (gas, liquid, solid).

Standard state pressure: 1 bar (105 Pa).

Standard state composition: the states of
pure species:-
Gases: ideal gas state at 1 bar.
Liquids and solids: the real liquid/solid at 1 bar.
 C is the standard-state heat capacity.

P
ig
It is identical to C .
P

Given the ammonia reaction:

1 3
N 2  H 2  NH 3 H 298

 46,110 J
2 2
N 2  3H 2  2NH 3 H 298

 92,220 J

The symbol H 298 indicates that the heat of



reaction is the standard value for a

temperature of 298.15 K (25°C).
 Standard Heat of Formation
Standard heat of any reaction can be
calculated if the standard heats of formation
of the compounds taking part in the reaction
are known.
A formation reaction is a reaction which
forms a single compound form its constituent
elements.
1
C  O 2  2H 2  CH 3OH from elements
2
H 2 O  SO 3  H 2SO 4 from other compounds
Heat of formation is based on 1 mol of the
compound formed.
Heat of reaction at any temperature can be
calculated for heat capacity data (Table C.1).

At temperature 298.15K (25°C), heat of

reaction can be calculated using standard heat
of formation, H f 298 for compounds from
Table C.4 in Appendix C.
Table C.4
Example 4.5

Calculate the standard heat at 25°C for the

following reaction:
4HCl(g)  O 2 (g)  2H 2 O  2Cl 2

Solution:
Standard heats of formation at 298.15K from
Table C.4 are:

HCl (g):-92,307 J H2O (g):-241,818 J

 Solution- continue:

4HCl(g)  2H 2 (g)  2Cl 2 (g) H 298


= (4)(92,307)

2H 2 (g)  O 2 (g)  2H 2 O(g) H 298


= (2)(-241,818)

4HCl(g)  O 2 (g)  2H 2 O(g)  2Cl 2 (g) H 298


= -114,408 J
 Standard Heat of Combustion

A combustion reaction is a reaction between an

element or compound and oxygen to form
specified combustion products.
Data are always based on 1 mole of the
substance burned.
 Example: The formation of n-butane is from
combination of combustion reactions.

4C(s)  4O 2 (g)  4CO 2 (g) H 298= (4)(-393,509)



1
5H 2 (g)  2 O 2 (g)  5H 2 O(l) H 298

= (5)(-285,830)
2
1
4CO 2 (g)  5H 2 O(l)  C 4 H10 (g)  6 O 2 (g) H 298

= 2,877,296
2

4C(s)  5H 2 (g)  C 4 H10 (g) H 298


= -125,790 J
2.4 Temperature Dependence of H


General chemical reaction:

 1 A1   2 A2  .....   3 A3   4 A4  .....
where  i are stoichiometric numbers and
Ai stands for a chemical formula.

The sign for  i is positive (+) for products and

negative (-) for reactants.
The sign allows the definition of a standard
heat of reaction.
Standard heat of reaction using stoichiometric
numbers:
H    i H i
i

where i is the enthalpy of compound i in its

H 

standard state. The summation,  is over all

products and reactants.
This enthalpy of compound i in its standard state,
H i is equal to its heat of formation, H f i plus


standard state enthalpies of its constituents

elements.
As the standard-state of enthalpies of elements
are set to zero as basic of calculation,

The enthalpy of compound i in its standard state,

H i is equal to its heat of formation.


Hence, the standard of heat of reaction;

H    i H f i
i
Example 4.5

Calculate the standard heat at 25°C for the

following reaction:
4HCl(g)  O 2 (g)  2H 2 O  2Cl 2

use H   i H
 
fi
i

H  2H
 
f H2O  4H 
f HCl

H  (2)(241,818)  (4)(92,307)  114,408 J



The answer is equal to previous solution !!

We have discussed the standard heat of
reaction for reference temperature 298 K.
Let us calculate the standard heat of
reaction at other temperature.
HOW???
By using the value at reference
temperature.
For standard reaction, products and reactants
are at standard pressure (1 bar).
The standard-state enthalpies are function of
temperature only. remember this?
dH  C dT
i
 
Pi

Multiplying by  i and summing over products

and reactants:

 i i  i Pi dT

i
dH 
  C 

i
Since  i is a constant, it may be placed inside
the differential:

 dH   C
i
i i


i
i

Pi dT d  i H i   i C Pi dT
i i

We already knew before that:

H   i H

i


Similarly, we can also define the standard heat

capacity as:
C P   i C Pi
 

i
Finally, we can get the fundamental equation
relating heats of reaction to temperature;

dH   C P dT
Heat of reaction
Integrating equation above; at 298 K.

T C
H  H  R 
 
0
P
dT
T0 R

Where H and H are heats of reaction at

 
0
temperature T and at reference temperature, T0.
 Solving the T C P would give:
T0 R dT
C P dT B 2 2 C 3 3 D    1 
   
T0 R   AT0   1  2 T0   1  3 T0   1  T0   
T

A  i  i Ai
where
similar with B , C and D .
T
remember… 
T0
For mean heat capacity of reaction,

C P B C 2 2 D
H
 A  T0   1  T0     1  2
R 2 3 T0

Hence, for heat reaction with mean heat

capacity,

H   H 0  CP H
T  T 
0
 Try by yourself..
Example 4.6

Calculate the standard heat of the methanol-

synthesis reaction at 800°C.
 Guide: H    i H f i
i

Which equation A  i  i Ai
should I use?
T

T0

B 2 2 C 3 3 D    1 
 AT0   1  T0   1  T0   1   
2 3 T0   

TC 
H   H 0  R  P
dT
T0 R
What have you learned…
 Heats effects in Industry

The applications of heat effects element

in industry are not as easy as you think!!

Sharpen your knowledge with

Example 4.7, Example 4.8 and Example 4.9.