Lecture6 PDF
Lecture6 PDF
Lecture6 PDF
Contents
Preamble
First law of thermodynamics
Various heat effects
Conclusions
References
Key words: thermo chemistry, Heat of formation, Heat of reaction, Kirchoff’s law
Preamble
All chemical processes involve various kinds of energy interchanges with the surrounding. Heat energy is
the principal form of energy exchange between metallurgical systems and its surrounding in various
extraction and refining of metals.
Thermo chemical calculations are required to perform energy balance of a process. Thermo chemical
calculations are concerned with chemical changes that are accompanied by liberation or absorption of
heat; for example
First law of thermodynamics:
In the following, only a brief account is given. The first law equation for a process occurring is a systems
is
∆E E E Q W
E and E are energy contents (internal energies) of the system in state 1 and state 2 (it must be clearly
understood that thermodynamics deals with initial and final states), Q is the heat absorbed by the
system from the surrounding and W is work done by the systems on the surrounding. Since E and
E depend only on final and initial state of a systems, change in energy ∆E is independent of the path.
Since ∆E is independent of the path, Q W is also independent of path. However Q and W represent
energy exchange with the surrounding and are not thermodynamic properties of the system. For
example, if for a given change in state by a path, heat Q absorbed is more than that path will also
correspond to more work, W.
Some of the paths treated in thermodynamics are constant pressure, econstant volume, adiabatic (Q=0)
and reversible ones. Extraction of metals is mostly carried at 1 atmospheric pressure. For constant
pressure processes, more useful form of first law can be derived.
The heat content or enthalpy of systems (H) is a thermodynamic property
H E PV (2)
P is pressure and V is volume of the system. With the help of equation 1, first law is written for any
thermodynamic change of state:
H H Q W P V P V (3)
For a constant pressure process, only expansion work is done by system on surrounding and is equal to
W P V V (5)
By 3,4 and 5 we get
H H Q or ∆H Q P (6)
In equation Q P is heat absorbed by system in changing from state 1 to state 2 by a path of constant
pressure. A change under constant pressure is 1 called “ISOBARIC process”.
If an isobaric processes involves work other than expansion
∆H QP W (7)
W1 does not include expansion work. For example in an electric process at constant pressure –W1 is
input of electrical work to the system.
The equation 6 is very useful since Q P is related to the heat content (H). The change in heat content ∆H
depends on the initial and final states only; hence heat absorption or evolution can be evaluated form
the data on the properties of system in the two states.
Various heat effects
a) Effect of temperature
The variation of heat content in pure compounds with temperature can be determined by
HT H aT bT cT d (8)
HT H is increase in heat content in cal/mole as the substance is heated from 298K to T. In all
calculations the reference temperature is 298K 25 or 77 . T is temperature in K and a, b, c and d
are constants and depends on state or aggregation of the system. The quantity HT H is called
sensible heat,
Molal heat capacity at constant pressure is
C a 2bT CT (9)
H T
C H H T
C dT (10)
P
Also change in heat content can be determined by mean heat capacity Cm
H H C T T (11)
T
T
C T
C (12)
T T
We may write
H H C T T (13)
Equation 13 may be used to calculate heat content for rapid calculations. More accurate would be to
use equation 8 or equations 9 and 10.
b) Changes in state of aggregation
When solid is heated to melting point additional heat must be supplied to melt it. At the melting print,
this additional heat does not increase the temperature. The heat content for melting at constant
pressure is called latent heat of fusion ∆H and this heat must be supplied at the melting point to
transform solid into liquid. An equal quantity of heat is liberated during solidification so that
∆H f ∆H (14)
Negative sign indicates liberation of heat. Similarly, heat effects accompanying evaporation and
allotropic changes in solids are measured by latent heat of vaporization and heats of transformation.
Value of ∆H for changes in state of aggregation vary with temperature and pressure under which change
is carried out. For example heat of vaporization of water at 1000C is 542cal/g, whereas it is 583 cal/g
at250C.
Example The melting point of Cu is 1357K.
c) Heat of formation
The formation of chemical compound from its elements is associated with either absorption or
liberation of heat. Thus the formation of H O l form the elements at 298K 25 can be written
H g O g H O l
∆H 68320 cal/mol at 1 atm pressure
d) Heat of reaction
∆H for any process depends only on the initial and final states and not on the path. If a process is
divided into several steps, and ∆H is determined for each step, the algebraic sum of the ∆H values of all
steps will be equal to ∆H for the original process. Consider an example to calculate heat of reaction of
the following reaction:
Fe O 3C 2Fe 3CO (1)
This reaction comprises of the following reactions:
C O CO ; ∆H° 29160
Heat of formation for reaction 1 at 298K is
∆H ° °
3 ∆HCO ∆HF° O (2)
It must be noted that heat of formation of element is zero by using the value of ∆H ° we get
Consider the reaction
∆H ° 3 ∆H ° CO
∆H ° F O
3 ∆H ° CO
∆H ° T
∆H ∑ HT H ∑ HT HT 15)
Conclusion
This lecture discusses the basics of thermo chemistry as required to calculate the different types of heat
associated with a chemical reaction. Heat of formation, latent heat of fusion, evaporation and
transformation are discussed and illustrated with a suitable example. Effect of temperature on heat of
reaction is also given. For details the readers may go through the references.
References:
Schuhmann: Metallurgical Engineering Principles
Alan and Geiger: energy balance in metallurgical processes