CHAPTER 4

Heat Effects

By: Wondimhunegn Misganaw

MSc. in Sustainable Energy Engineering

Debre Tabor, Ethiopia

2015 E.c.
Objectives
The objectives of Chapter 4 are to understand:
 Sensible heat effects, characterized by temperature changes
 Heat capacities as a function of temperature and their use
through defined functions
 Heats of phase transition, i.e., latent heats of pure substances
 Heats of reaction, combustion, and formation
 Heats of reaction as a function of temperature
 The calculation of heat effects for industrial reactions
Introduction
 Heat effects refer to physical and chemical phenomena that are
associated with heat transfer to or from a system or that result in
temperature changes within a system, or both.
 Chemical manufacturing processes may include a number of heat
effects.
• The oxidation reaction is
carried out near 250°C, and the
reactants must be heated to
this temperature, a sensible
heat effect.
• The oxidation reaction tends to
raise the temperature, and the
heat of reaction is removed
from the reactor to keep the
temperature near 250°C.
Sensible Heat Effects
 Heat transfer to or from a system in which there are no phase
transitions, no chemical reactions, and no changes in composition
causes a sensible heat effect.
 The specific internal energy of a substance may be expressed as a
function of two other state variables.

The final term is zero in two circumstances:

 For any closed-system constant-volume process.
 Whenever the internal energy is independent of volume, as for the ideal-
gas state and the incompressible liquid.
In either case,

For mechanically reversible constant-volume process

Cont.
 The enthalpy may be treated similarly

From the definition of 𝐶𝑝

Again, the final term is zero for two situations:

• For any constant-pressure process.
• When the enthalpy is independent of pressure, regardless of process.
This is exactly true for the ideal-gas state and approximately true for
real gases at low pressure and high temperature.
In either case,

Moreover, Q = ΔH for mechanically reversible, constant-pressure, closed-

system processes
Temperature Dependence of the Heat Capacity
 Evaluation of the integral in enthalpy(H) and (internal energy)U
requires knowledge of the temperature dependence of the heat
capacity.
 This is usually given by an empirical equation; the two simplest
expressions of practical value are:

where α, β, and γ and a, b, and c are constants

characteristic of the particular substance.
R is the universal gas constant 8.314 J/K.mol
We therefore combine them to provide a single expression:
Evaluation of the Sensible-Heat Integral
 Evaluation of the integral ∫ 𝐶𝑝 𝑑𝑇 is accomplished by substitution for
𝐶𝑝 as a function of T

• We identify the quantity in square brackets as 〈𝐶𝑝〉𝐻 /𝑅 , where

〈𝐶𝑝〉𝐻 is defined as a mean heat capacity for the temperature
range from T0 to T:

The equation for ∆H may therefore be written:

Given 𝑇0 and T, the calculation of Q or ΔH is straightforward. Less

direct is the calculation of T, given 𝑇0 and Q or ΔH. Here, an
iteration scheme may be useful.
Latent Heats Of Pure Substances
 When a pure substance under goes phase change at constant pressure,
no change in temperature occurs. however, these processes require the
transfer of finite amounts of heat to the substance. These heat effects are
called latent heats.

• Two phase system consisting of a single species is univariant, and its

intensive state is determined by the specification of just 1 intensive
property.
• Thus the latent heat accompanying a phase is a function of T only, and is
related to other system properties by an exact thermodynamics equation.
Clapeyron Equation
where for a pure species at temperature T,
ΔH = latent heat = enthalpy change accompanying the
phase change
ΔV = volume change accompanying the phase change
𝑃 𝑠𝑎𝑡 = saturation pressure, i.e., the pressure at which the
phase change occurs, which is a function only of T

 Latent heats are also measured calorimetrically. Experimental values are

reported at selected temperatures for many substances.
 When required data are not available, approximate methods can provide
estimates of the heat effect accompanying a phase change.
 Alternative empirical methods serve in:
 Predicting of the heat of vaporization at the normal boiling point i.e., at
a pressure of 1 standard atmosphere, define as 101,325 Pa.
 Estimating of the heat of vaporization at any T from the known value
at a single T.
Trouton’s rule
 Trouton gives rough estimates of latent heats of vaporization for
pure liquids at their normal boiling points (indicated by subscript n).
Trouton’s Rule where 𝑇𝑛 = Tabs of normal boiling point
∆𝐻𝑛 /R𝑇𝑛 = dimensionless
Experimental. Value: Ar=8.0; 𝑁2 =8.7; 𝑂2 =9.1;
𝐻𝐶𝑙=10.4; 𝐶6 𝐻6 =10.5; 𝐻2 𝑆=10.6; 𝐻2 𝑂=13.1

Riedel’s Equation
Also for the normal boiling point Riedel proposed an equation

where 𝑃𝑐 is the critical pressure in bars

𝑇𝑟𝑛 is the reduced temperature at 𝑇𝑛 .
This Equation is surprisingly accurate for an empirical expression; errors
rarely exceed 5 percent. Applied to water it gives:
H n 1.092(ln 220.5  1.013)
  13.56 This corresponds to 2334 J/g;
RTn 0.930  0.577 the steam-table value of 2257 J/g
is lower by 3.4 percent.
Hence, H  (13.56)(8.314)(373.15)  42,065 Jmol 1
Watson Method
 Estimates of the latent heat of vaporization of a pure liquid at any
temperature from the known value at a single temperature are given by
the method of Watson.
 The basis may be a known experimental value or a value estimated from
riedel’s equation

 This empirical equation is simple and fairly accurate

Example
Given that the latent heat of vaporization of water at 100°C is 2257 J⋅g−1,
estimate the latent heat at 300°C.
Solution
Standard Heat of Reaction ∆Ho298
 The enthalpy change of reaction ΔH is called the heat of reaction.
 If the reactants and products are in their standard states, then the
heat effect is the standard heat of reaction.
The definition of a standard state is
For a given temperature, A standard state is defined as the state of a substance
at specified pressure, composition, and physical condition as, e.g., gas, liquid, or
solid.
 The standard states in use is based on a standard-state pressure
of 1 bar (105 Pa).
 Consider reaction :

 The standard heat of reaction at temperature T is defined as the

enthalpy change when a moles of A and b moles of B in their
standard states at temperature T react to form l moles of L and m
moles of M in their standard states at the same temperature T.
Cont.
Symbols C Po Degree symbols = standard state
C Pig Ideal gas
Standard state of gases = ideal-gas state C o
P  CP
ig

 All conditions for a standard state are fixed except temperature, which is
always the temperature of the system. Standard-state properties are
therefore functions of temperature only.
 heat of reaction is applies for the stoichiometric coefficients as written. If
each stoichiometric coefficient is doubled, the heat of reaction is doubled.

The symbol ΔH°298 indicates that the heat of reaction is the standard value for a
temperature of 298.15 K (25°C) and for the reaction as written.
 Standard Heat of Formation
 A formation reaction is defined as a reaction that forms a single compound
from its constituent elements.

is a formation reaction for methanol

is not a formation reaction for sulfuric acid

Symbol °
∆𝐻 𝑓298
 The degree symbol denotes the standard-state value,
 Subscript f identifies a heat of formation, and
 the 298 is the rounded absolute temperature in kelvins.
• Formation reactions are understood to produce 1 mole of product; the
heat of formation is therefore based on 1 mole of the compound formed.
• Tabulation of data for just one temperature and for just the standard heats
of reaction for all of the vast number of possible reactions is impractical.
Some examples of
heat of formation :
Standard Heat of Combustion
 A combustion reaction is defined as a reaction between an element or
compound and oxygen to form specified combustion products.
 Many standard heats of formation come from standard heats of
combustion, measured calorimetrically.
 In some cases, heat of formation can be calculated from heat of
combustion (which is measurable),
 A reaction such as the formation of n-butane is not feasible in practice :

• However, this equation results from combination of the following

combustion reactions:

• This result is the standard heat of formation of n-butane listed in Table

C.4 of App. C.
Temperature Dependence of ΔH°
The general chemical reaction may be written as:
where νi is a stoichiometric coefficient
Ai stands for a chemical formula.
The sign convention for νi
positive (+) for products and negative (− ) for reactants

Standard heat of reaction

𝐻𝑖° : enthalpy of species i in its standard state
If the standard-state enthalpies of all elements set equal to zero as the basis
of calculation
Then standard heat of reaction

Example

With data from Table C.4 of App. C. for 298.15 K, this becomes:
 Cont.
Standard-state enthalpies are a functions of temperature only

For total products & reactants

=
The standard heat-capacity change of reaction is

From these definitions,

This is the fundamental equation relating heats of reaction to temperature

where ΔH° and 𝐻0° are the standard heats of reaction at temperature T and
at reference temperature 𝑇0 respectively.
 Cont.
If the temperature dependence of the heat capacity of each product and
reactant is given

where by definition,
with analogous definitions for ΔB, ΔC, and ΔD.
An alternative formulation results when a mean heat capacity change of
reaction is

Then ΔH° becomes

Figure : Path representing the

procedure for calculating a
standard heat of reaction at
temperature T from the value
at reference temperature 𝑇0 .
Heat Effects of Industrial Reactions
 The preceding sections have dealt with the standard heat of
reaction.
 Industrial reactions are rarely carried out under standard-state
conditions.
 In actual reactions the reactants may not be present in stoichiometric
proportions
 the reaction may not go to completion,
 the final temperature may differ from the initial temperature.
 inert species may be present, and
 several reactions may occur simultaneously.
 Nevertheless, calculations of the heat effects of actual reactions are
based on the principles already considered
Cont.
Cont.