Lecture 3

Enthalpy and its Application in Materials Processing

Thermodynamics of Materials -MME 221

Course Coordinator
Dr C SASIKUMAR, Assistant Professor
Department of Materials and Metallurgical Engineering (MME), MANIT Bhopal
Contact @ csasimv@gmail.com
ENTHALPY CHANGE IS A MEASURE OF HEAT ABSORBED OR EVOLVED
 Measurement in chemical, biological and physical systems at constant pressure
 Enthalpy – Sum of system’s internal energy and the product of its pressure and volume

 It is a state function
 Pressure and volume term is very small for solids and liquids

 By differentiating since

 At constant pressure dP = 0, thus

 Therefore, enthalpy is a stand-in energy for energy in chemical systems – bond, lattice, solvation and
other energies in chemistry
 As a state function enthalpy depends only on final configuration of E, P and V, not on the path taken to
achieve it.
 SI unit – Joules


ENTHALPY CHANGE IS A MEASURE OF HEAT ABSORBED OR EVOLVED …… cont.

 In chemistry, the standard enthalpy of reaction the enthalpy change when the reactants in
standard state (P = 1 atm., T = 298 K) change to products in their std. states.

 The quantity is the standard heat of reaction at const. pressure and temperature, but can be
measured by calorimetric methods, even if the temp. does not vary during the measurement,
provided that the initial and final pressure and temperature corresponds to std. state.

 Enthalpy is an extensive property ; it is proportional to the size of the system. The specific
enthalpy h = H/m is referenced to a unit of mass (m) of the system, and the molar
enthalpy Hm is H/n, where n is the number of moles.

 Enthalpy change is measured for large number of substances and processes and the data
may be obtained from CRC Handbook of Chemistry and Physics
ENTHALPY CHANGE IN MATERIALS PROCESSES
 Chemical Processes :
 Enthalpy of reaction - enthalpy change observed in a constituent of a thermodynamic system when
one mole of substance reacts completely.
 Enthalpy of formation - enthalpy change observed in a constituent of a thermodynamic system
when one mole of a compound is formed from its elementary antecedents.
 Enthalpy of combustion- enthalpy change observed in a constituent of a thermodynamic system
when one mole of a substance burns completely with oxygen.
 Enthalpy of atomization - enthalpy change required to separate one mole of a substance into its
constituent atoms completely.
 Standard Enthalpy of solution, - enthalpy change observed in a constituent of a thermodynamic
system when one mole of a solute is dissolved completely in an excess of solvent, so that the
solution is at infinite dilution.
 Enthalpy of hydration - enthalpy change observed when one mole of gaseous ions are completely
dissolved in water forming one mole of aqueous ions.
ENTHALPY CHANGE IN MATERIALS PROCESSES
 Physical processes :
 Enthalpy of fusion, defined as the enthalpy change required to completely change the state of one
mole of substance from solid to liquid.

 Enthalpy of vaporization, defined as the enthalpy change required to completely change the state
of one mole of substance from liquid to gas.

 Enthalpy of sublimation, defined as the enthalpy change required to completely change the state of
one mole of substance from solid to gas.

 Lattice enthalpy, defined as the energy required to separate one mole of an ionic compound into
separated gaseous ions to an infinite distance apart (meaning no force of attraction).

 Enthalpy of mixing, defined as the enthalpy change upon mixing of two (non-reacting) chemical
substances.
 THERMOCHEMISTRY AND ITS APPLICATIONS

Thermochemistry is the study of heat effects accompanying chemical reactions, the formation of
solutions and changes in the state of matter such as melting or vaporization, and other physico-
chemical processes.
ENTHALPY AS A FUNCTION OF TEMPERATURE AND COMPOSITION
We know that ………[1]

The enthalpy change for a closed system of fixed composition undergoing a change in Temperature from T 1 to
T2 at a constant pressure – by integrating eqn. [1]

Enthalpy change due to change of temperature of a

substance is known as sensible heat

∆H is thus area under the plot of Cp vs T between the

limits T1 and T2
and from ∆H = qp which is simply the amount of heat
required to increase the temperature of 1 mole of a system
From T1 to T2 at constant pressure
 HESS’S LAW

The law states that the heat content change in a chemical reaction is the same
whether it takes place in one or several stages, provided the temperature and
either pressure or volume remain constant.

ΔΗo, 298,(Reaction)

Iron
Hematite Fe
Fe203

Magnetite Wustite
MSME FeO
Fe 0
ENTHALPY CHANGE IN A CHEMICAL REACTION AT CONSTANT
TEMPERATURE AND PRESSURE
Consider a chemical reaction A + B = AB ………[1]

………[2]

is the difference between the enthalpy of the products and reactants

and eqn 2 is a statement of Hess’s law.

If is a positive quantity the reaction causes the system to absorb heat from the surrounding, and
the reaction is endothermic
if is a negative quantity the reaction occurs with evolution of heat thus an exothermic process.
ENTHALPY CHANGE IN A PHASE TRANSFORMATION

Consider the change of state A solid ↔ A liquid i.e. melting of pure metal A
………[2]

is the difference between the molar enthalpies of liquid and solid A at T 1.

Changes in enthalpy caused by changes in temperature and /or composition can be graphically represented on
enthalpy-temperature diagram. The change in enthalpy at T is reprn. by ba for the phase
1
occurring at T2 reprn. by line cd . Since H is a state function

+ -

where
ENTHALPY AS A FUNCTION OF TEMPERATURE WITH PHASE
TRANSFORMATION AND WITHOUT PHASE TRANSFORMTION
ENTHALPY CHANGE OF A SUBSTANCE WITHOUT ANY PHASE TRANSFORMATION/AGGREGATION

A,B,C,D are empirical constants

ENTHALPY CHANGE OF A SUBSTANCE IF THERE IS A PHASE TRANSFORMATION /AGGREGATION
Consider a pure substance A which is undergoing the following changes during heating from 298K to T ( OK)

A (Solid at 298 K ) → A (Liquid ) → A (gas at T)

ENTHALPY CHANGE OF A SUBSTANCE IF THERE IS A PHASE TRANSFORMATION/AGGREGATION

Consider a pure substance A which is undergoing the following changes during heating from 298 to T OK
A (Solid at 298 K ) → A (Liquid ) → A (gas at T)
Enthalpy Change, ∆H0

Solid Liquid gaseous

298 Tm Temperature (K) Tb T
 Heating and Cooling curves of Pure Iron

1600 1540

δ-Fe
1400

PM
1395, AC4 1395, Ar4

on c
Temperature, oC

ooli
1200

Non-Magnetic

ng
γ-Fe
ng

PM
ooli

1000
on c

898
910
Ar3
β-Fe

800 760 AC3 760

PM

Ac 2 Ar2
600
Magnetic
α-Fe
FM

400

200
Time 
Transformation Temperature : Notation
 Ac1 The temperature at which austenite begins to form during heating
 Ac2 The temperature at which α-iron changes to non-magnetic β-iron
 Ac3 The temperature at which α-iron to austenite is completed during heating
 Ac4 The temperature at which austenite transforms to delta ferrite on heating
 Acm In hypereutectoid steel, the temperature at which the solution of cementite in austenite is completed
during heating.
 Ar1
 Ar2
 Ar3
 Ar4
 Arcm
 Thermal Hysteresis in heating – The transformation occurs at much higher temperatures on heating and
lower temperature on cooling under normal heating or cooling rate.
 Recalescence – This is revealed by re-glowing of the surface due to the sudden
Increase in the temperature caused by quick liberation of latent heat of transformation.
 Decalescence –sudden decrease in the temperature due to reverse phase change.
ENTHALPY CHANGE AS A FUNCTION OF TEMPERATURE FOR IRON
Enthalpy Change, ∆HO

α-Fe β-Fe γ- Fe δ- Fe Liquid- Fe

MSME
HEAT REQUIRED TO RAISE THE TEMPERATURE OF IRON FROM 298K TO 1873 K
Calculate the heat required per kg to raise the temperature of steel scrap from 25°C (298 K) to 1600°C (1873 K)
from the following data given for iron :

( i ) Iron undergoes solid state transformation at 760°, 910° and 1400°C (1033, 1183 and 1673 K) with heat of
formation of 326, 215 and 165 cal/mole (1,364, 900 and 690 J/mol) respectively.

( ii ) Melting point of iron is 1537°C (1810 K) and heat of fusion is 3,670 cal /mole (15,355 J/mol).

( iii ) Temperature range CP,Fe

25°C - 760°C (298 - 1033 K)
760° - 910°C (1033 - 1183 K)
910°-1400°C(1183 - 1673 K)
1400° - 1537°C (1673 - 1810 K)
1537 -27000C (1810 - 2973 K)
(iv) Atomic weight of iron = 55.85.
3.0 + 7.58 x 10-3 T + 0.6 x 105 T-2cal/deg/mole
(12.55 + 31.71 X 10-3T + 2.51 X 105 T-2 J/K/mol)
11.13 cal/deg/mole
(46.57 J/K/mol)
5.80 + 2.0 x 10-3 T cal/deg/mole
(24.27 + 8.37 X 10-3 T J/K/mol)
6.74 + 1.64 x 10-3 T cal/deg/mole
(28.20 + 6.86 X 10-3 T J/K/mol)
9.77 + 0.40 x I0-3 T cal/deg/mole
(40.88 + 1.67 X I0-3 T J/K/mol)
 Education is the ability to listen to
almost anything without losing your
temper or your self-confidence