S. S.

AGRAWAL INSTITUTE OF ENGINEERING & TECHNOLOGY [123]

Chemical Engineering Thermodynamics I (3130507)

Ch 3 :Heat Effects

Prepared by
Heena N Katariya
Assistant Professor
S. S Agrawal Institute of Engineering & Technology
Contents
• Sensible heat effects
• Temperature dependence of the heat capacity
• Latent heats of pure substances
• Approximate methods for the estimation of the
latent heat of vaporization
• Standard heat of reaction, standard heat of
formation, standard heat of combustion
• Temperature Dependence of ΔH⁰
• Heat effects of Industrial Reactions.
Sensible heat effects
• When the system is a homogeneous substance of constant composition, the phase rule indicates
that fixing the values of two intensive properties establishes its state.
• The molar or specific internal energy of a substance may therefore be expressed as a function of
two other state variables. These may be arbitrarily selected as temperature and molar or specific
volume:
• 𝑈 = 𝑈 𝑇, 𝑉 …………………………………………………………………….(1)
𝜕𝑈 𝜕𝑈
• 𝑑𝑈 = ( )𝑉 𝜕𝑇 + ( ) 𝑇 𝜕𝑉……………………………………………….(2)
𝜕𝑇 𝜕𝑉
𝜕𝑈
• 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + ( ) 𝑇 𝜕𝑉…………………………………………………….(3)
𝜕𝑉
• The final term may be set equal to zero in two conditions
(1) For any constant-volume process, regardless of substance
(2) Whenever the internal energy is independent of volume, regardless of the process.
• This is exactly true for ideal gases and incompressible fluids and approximately true for low
pressure gases,
• 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝑇
• And ∆𝑈 = 𝑇 2 𝐶𝑉 𝑑𝑇--------------------------------------------(4)
1
• For mechanically reversible constant volume process, 𝑄 = ∆𝑈,
𝑇2
• 𝑄 = ∆𝑈 = 𝑇1 𝑉
𝐶 𝑑𝑇
• Similarly for constant pressure process
𝑇2
• 𝑄 = ∆𝐻 = 𝑇1 𝑝
𝐶 𝑑𝑇
 Temperature Dependence of the Heat
capacity
𝑇
• 𝑄 = ∆𝐻 = 𝑇 2 𝐶𝑝 𝑑𝑇--------------------------------------------(1)
1
• Evaluation of the above integral requires knowledge of the temperature
dependence of the heat capacity.
• This is usually given by an empirical equations; the two simplest
expressions of practical value are
𝐶𝑃
• = 𝛼 + 𝛽𝑇 + 𝛾𝑇 2 , and……………………………………………..(2)
𝑅
𝐶𝑃
• = 𝑎 + 𝑏𝑇 +
𝑅 −2
𝑐𝑇 ……………………………………………………..(3)
• Where 𝛼, 𝛽, 𝑎𝑛𝑑 𝛾 𝑎𝑛𝑑 a,b, and c are constant of the particular
substance.
• With the exception of the last term, these equations are of the same form,
then in a single expression:
𝐶
• 𝑅𝑃 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + D𝑇 −2 ------------------------------------(4)
• Where either C or D is Zero , depending on the substance considered.
𝐶𝑃
• Because the ratio 𝑅
is dimensionless, the units of 𝐶𝑃 are governed by
the choice of R.
Latent heats of pure substances
• When a pure substance is liquefied from the solid state or vaporized from liquid
at constant pressure, no changes in temperature occurs, the process requires the
transfer of finite amount of heat to the substance. These hat effects are called the
latent heat of fusion and the latent heat of vaporization.
• Phase changes such as fusion, vaporization and condensation are accompanied by
large changes in enthalpy.
• When matter undergoes a phase change (vapor to liquid, liquid to solid,etc), the
enthalpy change associated with unit amount of matter at constant temperature
and pressure is known as the latent heat of phase change.
• Latent heat of phase changes are defined as follows:
• Latent heat of vaporization: it is the heat required to vaporize a unit amount of
liquid at constant temperature and pressure.
• Latent heat of Fusion: it is the heat required to melt a unit amount of solid to
liquid or heat removed to convert unit amount of liquid into solid at constant
temperature and pressure.
• Latent heat of sublimation: it is the heat required to vaporize a unit amount of
solid at constant temperature and pressure.
Approximate methods for the estimation
of the latent heat of vaporization
• Approximate methods are used for estimates of the heat effect accompanying
phase change (latent heat).
1. Rough estimates of latent heat of vaporization for pure liquids at their normal
boiling points are given by Trouton’s rule:
∆𝐻𝑛
~10
𝑅𝑇𝑛
• Where, 𝑇 is the absolute temperature of the normal boiling point.
∆𝐻𝑛
• The units of ∆𝐻. R and T must be chosen so that 𝑅𝑇𝑛
is dimensionless.
2. Another method is proposed by Riedel.
∆𝐻𝑛 1.092(𝑙𝑛𝑃𝐶 − 1.013)
=
𝑅𝑇𝑛 0.930 − 𝑇𝑟𝑛
• Where 𝑃𝐶 is the critical pressure in bars and 𝑇𝑟𝑛 is reduced temperature at 𝑇𝑛 .
3. Estimates of the latent heat of vaporization of pure liquid at any temperature
from the known value at a single temperature may be based on a known
experimental value or on a value estimated by Riedel equation. The method
proposed by Watson has found wide acceptance.
0.38
∆𝐻2 1 − 𝑇𝑟2
=
∆𝐻1 1 − 𝑇𝑟1
 Enthalpy changes accompanying Chemical
reactions
• Whenever a chemical reaction takes place, heat may either be evolved or absorbed and
this heat plays important role in the economics of chemical process.
• Heat of Reaction: it is the enthalpy change resulting due to a chemical reaction
wherein: (i) the reactants are fed in the stoichiometric amounts and the reaction
proceeds to completion (ii) the reactants are fed at temperature T and pressure P, and
the products emerge at the same temperature and pressure.
• The Standard Heat of Reaction: it is the enthalpy change associated with a chemical
reaction when both reactants and products are in their standard states. It is denoted
by∆𝐻°𝑅 .
• Heat of Formation: it is the enthalpy change accompanying the formation of one
mole of a compound from its element at a given temperature and pressure.
• The Standard Heat of formation: it is the heat of reaction when one mole of a
compound is formed from its element in a reaction beginning and ending at 298.15 K
and at pressure of 0.1 [Link] is denoted by ∆𝐻°𝑓 .
• Heat of Combustion: it is the heat of reaction of one mole of substance with
molecular oxygen.
• The Standard Heat of Combustion: it is the heat of reaction of substance with
molecular oxygen to yield specified products with both reactants and products are at
their standard state. It is denoted by ∆𝐻°𝐶 .
 Hess’s Law of Constant Heat
Summation
• The net heat evolved or absorbed in a chemical reaction is the same whether the
reaction takes place in a single step or in a series of steps. This is known as
Hess’s law.
• Hess’s law permits us to treat all thermochemical equations as algebraic
equations.
• Using this, we can calculate the heat of formation of a compound from a series of
reactions not involving the direct formation of the compound from its elements
• For example, the heat of formation of a compound can be calculated, if the heat
of combustion data of all the species involved in the formation reaction are
known.

• Similarly, if the data on the heat of formation of all the substances taking part in a
chemical reaction are available, the heat of reaction may be readily calculated.

• The standard heats of formation of elements are taken as zero.