Chapter 4 Heat Effects

4.1 Sensible Heat Effects

4.2 Latent Heats of Pure Substances
4.3 Standard Heat of Reaction
4.4 Standard Heat of Formation
4.5 Standard Heat of Combustion
4.6 Effect of Temperature
4.7 Heat Effects of Industrial Reactions

Manufacture of Ethylene Glycol: (CH2OH)2

(1) Catalytic oxidation of ethylene to ethylene oxide
The catalytic oxidation process is most effective when carried out at temperatures near 250oC. The
reactants, ethylene and air, are heated to 250oC before they enter the reactor. The design of the
preheater requires the calculation of heat required (sensible heat).
The reaction of ethylene with oxygen liberates heat that tends to raise the temperature of catalyst
bed (heat of reaction). To maintain the temperature at around 250oC, heat is removed from the reactor.
Higher temperatures promote the production of CO2, an undesired product. The design of reactor
requires knowledge of heat effects associated with chemical reactions.

(2) Hydration of ethylene oxide to glycol

The ethylene oxide formed is hydrated to glycol by absorption in water. This is accompanied by
evolution of heat as a result of the phase change (latent heat), the formation of a solution (heat of
solution) and the hydration reaction between the dissolved ethylene oxide and water (heat of reaction)

(3) Recovery of glycol

Finally, the glycol is removed from water by distillation, a process requiring vaporization of a liquid
mixture that results in the separation of the mixture into components.

Sensible Heat Effects

Sensible heat is heat transfer resulting in a temperature change in the system with no phase
transitions, no chemical reactions and no changes in composition are involved.

(1) or is used
(a) For any constant-pressure process, regardless of the substance.
(b) Whenever the enthalpy of the substance is independent of pressure, regardless of the process.
(c) Transfer of heat in steady-flow systems where PE, KE and Ws = 0.

(2) or is used
(a) For any constant-volume process, regardless of the substance.
(b) Whenever the internal energy of the substance is independent of volume, regardless of the
process.

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Temperature Dependence of Heat Capacities of Gases

The temperature dependence [Cp=f(T)] is given by an empirical equation. The two simplest
expressions of practical value are
(a) Cp/R =  + T + T2
(b) Cp/R = a + bT + cT-2
Where ,  and, a, b and c are constants characteristic of particular gas.

The two equations are combined to provide a single expression:

Where C or D is zero depending on the gas considered. Values of A, B, C and D are obtained from Table
C.1/pp684-685. SVNA (7th ed).
Since – then

T2

H  C
ig
P dT
T1

C Pig
 A  BT  CT 2  DT  2
R

Mean heat capacities (for enthalpy calculations):

H  C P H
T2  T1 
T2

C P dT

T1
CP H
T2  T1 
CP
R
H
 A  BTam 
C
3
 2
4Tam 
 T1T2 
D
T1T2

Example 4.1
Example 4.2
Example 4.3

Latent Heats of Pure Substances

Latent heat is a heat transfer resulting in a phase change of system at constant
temperature and pressure.

Clapeyron Equation
The latent heat accompanying a phase change is a function of temperature and is
related to other system properties by the Clapeyron Equation:

(dP/dT) = H/TV (for a pure species at temp T)

H = latent heat
V = volume change accompanying the phase change
P = vapor pressure

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Vaporization of a Liquid
When the Clapeyron equation is applied to the vaporization of a pure liquid, dP/dT is the slope
of the vapor pressure-temperature curve at the temperature of interest, V is the difference between
the molar volumes of saturated vapor and saturated liquid and H is the molar latent heat of
vaporization.
The equation is also valid for other phase changes (eq., solid to liquid).

Approximate Methods for Evaluating Latent Heat of Vaporization

The data necessary for the application of the Clapeyron equation are usually not available. In this
event, approximate methods are used to evaluate latent heats.
(1) Riedel Equation

 –
–

Tn = normal boiling point (K)

Hn = molar heat of vaporization at Tn
PC = critical pressure (bar)
Trn = reduced temperature at Tn

(2) Watson Equation


[ ]


H1 = latent heat of vaporization at T1

H2 = latent heat of vaporization at T2
Tr1 = reduced temperature at T1
Tr2 = reduced temperature at T2

Example 4.4

Heats of Reaction

Thermochemical Equation
A thermochemical equation gives the quantity of heat associated with a given reaction and
indicates all the conditions given below.
(a) the quantity that reacts
(b) temperature of reaction (all substances involved in the reaction must be at the indicated
temperature)
(c) the physical state of each reactant and product
(d) whether the reaction occurs at constant volume or at constant pressure.

Examples:

H2(g) + ½ O2(g)  H2O(g) H25oC = -57800 cal/g-mol

H2(g) + ½ O2(g)  H2O(l) H25oC = -68320 cal/g-mol

H2(g) + ½ O2(g)  H2O(l) U25oC = -67432 cal/g-mol

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Note: If not specified, a given heat of reaction is understood to be at 25oC and at constant pressure. The
heat of reaction or the enthalpy change at these conditions is called the standard heat of reaction,
Ho298.

Heat of Formation
The heat involved in the formation of one mole of a compound from its constituent elements.
The heat of formation of an element is zero. The heat of formation of a compound maybe
obtained by:
(a) direct measurement of the H of the reaction of the formation of the compound from its
constituent elements.
(b) calculation from heats of reaction involving the compound.

Standard Enthalpies of Formation at 25oC: Table C.4 of App.C.

Heat of Reaction from Standard Heats of Formation of Reactants and Products

HRxn = nHfproducts - nHfreactants

Example 4.5
Calculate the standard heat at 25oC for the following reaction:

4 HCl (g) + O2 (g)  2 H2O (g) + 2 Cl2 (g)

Heat of Combustion

The heat of combustion of a substance is the heat liberated in the complete combustion of 1.0
mol of the substance (element or compound).
Heat of combustion is always negative since heat is always given off and it can directly be
measured by the combustion reaction itself.

Application of Heats of Combustion

(a) to determine the suitability of a substance as an industrial fuel with respect to heat
evolved on combustion
(b) to calculate heats of formation of substances whose formation reactions cannot be carried
out experimentally
(c) heat of reaction in cases where the heat of formation of reactant or product is not
available
(d) energy differences of allotropic forms of elements
(e) energy associated with certain atomic groups in a molecule.

Higher Heat of Combustion and Lower Heat of Combustion

If H2O is a product of combustion, the higher heat of combustion is obtained when the H2O
product is in the liquid state and the lower heat of combustion is when the H2O product is in the vapor
state.

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Hess Law of Heat Summation

Internal energy and enthalpy are functions of the state of the system only. Thus, the heats of
reaction, U and H depend only on the initial and final states of the system. It is not affected by the
number of steps between reactants and products.
If a reaction proceeds in several steps, the heat involved in the overall reaction is the algebraic
sum of the various steps and this sum will be identical with the heat involved if the reaction proceeds in a
single step. This generalization is known as Hess Law.

Example: From the following heats of combustion,

CH3OH(l) + 3/2 O2(g)  CO2(g) + 2H2O(l) Ho = -726.4 kJ

C(graphite) + O2(g)  CO2(g) Ho = -393.5 kJ
H2(g) + ½ O2(g)  H2O(l) Ho = -285.8 kJ

Calculate the enthalpy of formation of methanol from its elements:

C(graphite) + 2H2(g) + ½ O2(g)  CH3OH(l)

Heat of Reaction as a Function of Temperature

The heat of reaction obtained calorimetrically or by calculation corresponds to some one

definite temperature. All other temperatures, the heat of reaction will usually not be the same.

For a reaction:
H = Hproducts - Hreactants
On differentiation of both sides with respect to absolute temperature at constant pressure yields
[(H)/T]P = [Hproducts/T]P – [Hreactnts/T]P but [H/T]P = Cp

= Cpproducts - Cpreactants
= Cp

And equation expressed in differential form is

d(H) = CpdT
H T
2 2
To evaluate by integration d(H) = CpdT
H T
1 1
T
2
H2 = H1 + CpdT
T
1

H2 = H1 + Cpmh(T2 – T1)

Example 4.6

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Heat Effects of Industrial Reactions

In industrial reactions,
(a) the reactants may not be present in stoichiometric proportions
(b) reaction may not go to completion
(c) final temperature may differ from the initial temperature
(d) inert species may be present
(e) several reactions may occur simultaneously
Example 4.7
Example 4.8
Example 4.9

Example 4.8, on p. 144 illustrates situation where there is a change in number of moles, and
where two chemical reactions take place.

The first heat effect (sensible heat) represents the enthalpy of the reactant stream in the
standard state minus the enthalpy of this stream in the actual inlet state.

The second and third heat effects (heats of reaction) are the enthalpy changes on reactions in
the standard state.

The fourth heat effect (sensible heat) represents the enthalpy of the product stream above the
standard state (i.e., the enthalpy of the product stream in the actual outlet state minus the
enthalpy of this stream in the standard state).

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