ChE 226 2013 Chapter 4

1


Heat Effect, Part 1: Sensible Heat and latent Heat

Overview:
Sensible heat effects(changing the temperature of a substance)

o Computing changes in internal energy using C
v
:
=

1

o Computing changes in enthalpy C
p
:
=

1

o Evaluating these integrals with heat capacities expressed as polynomials
o Extension to fluid mixtures
Latent heats of pure substances (changing the phase of the substance)

When we transfer heat into (or remove heat form) a fluid, this energy might be used (in whole or in part)
to do work on the surroundings, to change the temperature of the fluid, to change the phase of the fluid, or
to provide the energy required to carry out a chemical reaction. In this chapter, these heat effects are
discussed.

Sensible Heat Effects

The first heat effects that we will consider are called sensible heat effects because they involve heating or
cooling that changes the temperature of the system. If we consider a closed system, where there are no
phase transitions, no chemical reactions, and no changes in the composition of the system, then adding
heat to or removing heat from the system will change its temperature and/or cause it to do work on the
surroundings. Our goal is to relate the temperature change and work done to the amount of heat added.
For a homogeneous substance of constant composition, the phase rule tells us that two intensive
properties must be fixed to specify the state of the fluid completely. Thus the internal energy or enthalpy
can be written as a function of two intensive variables, like temperature, pressure, and molar volume.
Thus, using T and V as the independent variables for U, we write

= (, )

and =

where we have used the definition of C
v
that we have already discussed in previous lectures.

The last term (the term) is zero for:
Any constant-volume (isochoric) process, with any type of fluid;
Any fluid whose internal energy does not depend on molar volume, i.e.
o Ideal gases
o Incompressible liquids
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In those cases, we have
=

1



Similarly for enthalpy, we write
= (, )

and =

where we have used the definition of C
p
that we have already discussed.

The last term (the term) is zero for
Any constant-pressure process, with any fluid
Any fluid whose enthalpy does not depend on pressure, e.g. ideal gases, Incompressible
liquids

In those cases, we have simply
=

1

Furthermore, we know that for constant-volume processes, = , and for constant-pressure processes,
= . This lets us calculate things like the amount of heat required to change the temperature of a
substance by a certain amount.

Heat capacities are often expressed in the form of polynomials in temperature, or as other simple
functions. The form used in SVA most commonly is

= + +
2
+
2


Note that for ideal gases, C
v
and C
p
are related by

+
So for an ideal gas, if C
p
is given by the form shown above, then C
v
is given by

= 1 + +
2
+
2


For incompressible fluids, C
v
and C
p
are the essentially the same (a constant pressure process on an
incompressible substance is also a constant-volume process, since the volume is essentially constant for
an incompressible substance).


The above form of the heat capacity is easily integrated - for example
ChE 226 2013 Chapter 4
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=

= ( + +
2
+
2
)

1


= (
2

1
) +

2
(
2
2

1
2
) +

3
(
2
3

1
3
) (
1

2

1

1
)

SVA also give a representative computer program for doing such calculations in Appendix D.

For mixtures of gases at low pressure, one can simply take the heat capacity of the mixture as the
average of the heat capacity of the components, weighted by their mole fractions in the mixture. That is, if

is the mole fraction of species i in the mixture, then the molar heat capacity of the mixture is simply

,



Latent Heats of Pure Substances

When a pure substance is converted from one phase to another (solid to liquid, liquid to vapor, etc.) heat
flows to or from the substance, but there is no change of temperature. The energy per mole required to
vaporize a liquid is called the latent heat of vaporization, and the energy per mole required to melt a solid
is called the latent heat of fusion. We know from the phase rule that for a 1-component, 2-phase system,
specifying one intensive variable specifies the state of the system. Thus, the latent heat of a phase change
is a function only of one intensive variable, and can therefore be written as a function of temperature
alone. This function can be written as

=

where is the latent heat for the phase change (the difference between the molar enthalpies of the two
phases), is the volume change for the phase change (big for vaporization; small for melting), and

is the pressure of the two-phase system (which is a function only of temperature, since specifying the
temperature specifies all other intensive properties of the 2-phase system). For a vaporization phase
change,

is the vapor pressure of the liquid. This equation is called the Clapeyron equation. So, to get
the heat of vaporization, we could either make a direct measurement (using a calorimeter),or we could
compute it from the vapor pressure curve and the volumetric properties of the liquid and gas. Some
correlations for estimating heats of vaporization are given on p.134 of SVA.

Troutons rule can be used to obtain rough estimates of latent heats of vaporization for pure liquids at
their normal boiling points (i.e., at P =1 atm):

~10

Where T
n
is the absolute temperature corresponding to the normal boiling point of the substance.
Representative experimental values for this ratio are:
Ar: 8 N
2
: 8.7 O
2
: 9.1 HCl: 10.4 C
6
H
6
: 10.5 H
2
S: 10.6 H
2
O: 13.1

A more accurate empirical equation has been proposed by Riedel:
ChE 226 2013 Chapter 4
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= [1.092(

1.013)/(0.930

)]
where P
c
is the critical pressure of the substance and

the reduced temperature at T

n

Finally, Watson proposed a fairly accurate equation for estimating the latent heat of vaporization of a
pure liquid at any temperature T
2
from a given value at a single temperature T
1
:

1
= [(1
2
)/(1
1
)]
0.38


where
1
= (

)and
2
= (

)are the corresponding reduced temperatures.

Summary:

After completing your study of these lecture notes and the associated homework and material from
Chapter 4 of SVA, you should be able to:
Use C
p
or C
v
to compute changes in H or U, respectively, using a heat capacity integral;
Compute heat capacity integrals with non-constant C
p
expressed as a polynomial
in temperature;
Use heat capacity integrals to find the energy input required to affect a given temperature
change or temperature change resulting from a given energy input;
Look up or estimate latent heats for phase changes and apply then to compute the energy
input required to change the phase of a substance;

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Heat effects, Part 2: Heats of Reaction

Overview:
Heat of reaction (enthalpy change for reaction)
Heat of formation (enthalpy of formation)
Heat of combustion
Temperature dependence of heat of reaction

So far, the heat effects we have discussed (sensible heat and latent heat of pure substances) have been for
physical processes (processes where no chemical reactions occur). In fact, pretty much everything that we
have done so far this semester has been for physical processes. However, as you might guess, chemically
reacting systems are an important part of chemical engineering. Heat effects due to chemical reaction can
be quite large compared to those associated with physical processes. During a chemical process, energy is
stored in and released from the chemical bonds that form between atoms in molecules. Since these bonds
are, usually, much stronger than the physical interactions between molecules, they can store and release
much greater amounts of energy.

Consider an isothermal flow calorimeter for measuring the heat released or consumed by reaction.
In such a device, a stoichiometric mixture of reactants flows in and reacts, and we measure the heat
(addition or removal) required to return the reaction products to the inlet temperature of the reactants.



The process is carried out at constant pressure, and no non-flow work is done, so

=


That is, the heat added or removed is equal to the change in enthalpy of the stream flowing
through the calorimeter. This, in turn, is equal to the difference in enthalpy between the products and the
reactants, at constant temperature. The heat of reaction for the reaction is defined as this change in
enthalpy at constant temperature.

Now, consider the generic balanced chemical reaction

+ +

The standard heat of reaction for this reaction at temperature T is defined as the enthalpy change when
a moles of A plus 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. A standard state is a particular state of a
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species at temperature T and at specified conditions of pressure, composition, and physical condition (e.g.
gas, liquid, or solid).

In SVA, the standard states for computing heats of reaction are:

Gases: the pure substance in the ideal-gas state at 1 bar.
Liquids and solids: the pure substance at 1 bar.

Older data tabulations often use 1 atm rather than 1 bar as the standard pressure, but this makes a
negligible difference for most applications.

It is particularly important to note and remember that the heat of reaction is defined for the particular set
of stoichiometric coefficients of the reaction. For example, we could write the reaction for the partial
oxidation of methane to CO and H
2
(this mixture is called synthesis gas or syngas for short) as

CH
4
+1/2O
2
CO+2H
2
or as
2CH
4
+O
2
2CO+4H
2

Either of these forms is a valid way to write the reaction, but the heat of reaction for the second version is
twice that of the first version, so it is important that we know which version of the reaction is being used.
To summarize, the heat of reaction can only be interpreted with respect to a particular writing of the
reaction.

Standard Heats of Formation:

It would be impossible (or at least impractical) to tabulate the heats of reaction for all possible reactions
of interest. Fortunately, they can be calculated from a standard set of heats of reaction. This set consists
of theheats of formation of the chemical species.

The heat of formation of a substance is defined as the heat of reaction when the substance is formed
in its standard state at temperature T, from elements in their standard states at temperature T.

For example, the heat of formation of ethanol (CH
3
CH
2
OH) is equal to the heat of reaction of

2C(s)+3H
2
(g)+1/2O
2
(g) CH
3
CH
2
OH(l)

This is the formation reaction for ethanol from elements in their standard states. In this hypothetical
reaction, two moles of graphite (the standard state of carbon) plus 3 moles of hydrogen gas plus one-half
of a mole of oxygen gas react to produce one mole of liquid ethanol. Heats of formation are defined as the
heat of reaction per mole of the species formed, and, therefore, these reactions are written so that the
stoichiometric coefficient of the species formed is one.




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What makes heats of formation useful is the fact that we can write any reaction as the sum of
formation reactions. Consider again the partial oxidation of methane to synthesis gas

CH
4
+1/2O
2
CO+2H
2

This can be written as the sum of the following formation reactions:
C+1/2O
2
CO
CH
4
C+2H
2
CH
4
+1/2O
2
CO+2H
2


Note that we dont need to include formation reactions for H
2
or O
2
, since they are elements. The heats of
formation of elements are zero by definition. They form the reference point for defining the heats of
formation of everything else.

The heat of reaction of the first reaction (C+1/2O
2
CO) is the heat of formation of CO (H
f
(CO)).
Notice that the reverse of the second reaction is the formation reaction of methane. As a result, the heat of
reaction of the second reaction is minus the heat of formation of CH
4,
i.e. (-H
f
(CH
4
)). Reversing the
direction of the reaction reverses the sign of the heat of reaction. So, the heat of reaction for the partial
oxidation is:

()

(
4
)

In general, any heat of reaction can be computed as the heat of formation of the products minus the heat
of formation of the reactants. That is, for the generic reaction

+ +

the heat of reaction is:

() +

()

()

()

Thus, if we have a table of the enthalpies of formation of species (at some standard temperature),
then we can compute the heat of reaction for any reaction involving those species (at the same
standard temperature). As we mentioned already, the heats of formation of elements are zero by
definition. They form the reference point for defining the heats of formation of everything else. Usually,
heats of formation are tabulated at a standard temperature of 298 or 298.51K. To get heats of formation or
heats of reaction at other temperatures, we must integrate the heat capacities of the reactants and products
to see how the enthalpies of the reactions and products change with temperature.

Heats of Combustion:

Most formation reactions cannot actually be carried out in practice. For example, we probably could not
devise a calorimeter where we form ethanol (in 100% yield) from a stoichiometric mixture of graphite,
hydrogen, and oxygen. So, heats of formation usually have to be determined from calorimetric
measurements that can easily be carried out. The most common class of reactions that goes nicely to
completion is combustion reactions. Imagine that we have a flow calorimeter in which we can burn
things. Then we could first burn some hydrogen

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H
2
(g)+1/2O
2
(g)H
2
O(l)


From which we could get the heat of formation of water (this is a formation reaction that we can measure
directly). Next, we might be able to burn some graphite directly, as

C(s)+O
2
(g)CO
2
(g)

From which we would get the heat of formation of CO
2
(this is another formation reaction that we can
measure directly). Knowing these, we could boldly start burning all sorts of compounds made up of only
C, H, and O, and could determine their heats of formation from the heats of reaction for the combustion
reaction

C
x
H
y
O
z
+(x+1/y-1/2z)O
2
(g)xCO
2
(g)+1/2yH
2
O(l)

and the known heats of formation for carbon dioxide and water. This particular heat of reaction (1 mole of
the substance burned plus a stoichiometric amount of oxygen to carbon dioxide and water) is known as
the heat of combustion of the material.
For example, we could burn ethanol completely

CH
3
CH
2
OH(l)+3O
2
(g)2CO
2
(g)+3H
2
O(l)

The standard heat of reaction for this reaction at 298 K is

,298
= 2
,298

(
2
(g)) +3
,298

(
2
())
,298

(
3

2
())

This is the heat of combustion for ethanol. So, we might also write it as

,298
(
3

2
()) = 2
,298

(
2
(g)) +3
,298

(
2
())
,298

(
3

2
())

Note that in these reactions we have explicitly indicated the phase (s for solid, l for liquid, or g for gas)
that corresponds to the standard state for each species.

From the above relationship between the heat of formation and the heat of combustion, we have

,298
= 2
,298

(
2
(g)) +3
,298

(
2
())
,298

(
3

2
())

Idea: So, lets imagine for a moment that we dont know the heats of formation of anything, but we have
a flow calorimeter that we operate at a constant pressure of 1 bar and an inlet and outlet temperature of
25
o
C. We perform the following experiments in our calorimeter:

We first burn H
2
gas and find a heat of combustion of -285.8kJ /mol.
Next, we burn graphite powder (C) and find a heat of combustion of -393.5kJ /mol.
Finally, we burn liquid ethanol (CH
3
CH
2
OH)and find a heat of combustion of -1366.7kJ /mol

The formation reactions for H
2
O and CO
2
are the same as the combustion reactions of H
2
and C,
respectively, so the heats of formation for H
2
O and CO
2
are equal to the heats of reaction that we
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measure for the H
2
and C combustion reactions (both are at the same standard state conditions of 25
o
C
and 1 bar). So, we get

H
2
(g)+1/2O
2
(g)H
2
O(l)

,298
=
,298

(
2
()) = 285.8 kJ/mol
C(s)+O
2
(g)CO
2
(g)

,298
=
,298

(
2
()) = 393.5 kJ/mol

Then, we can compute the heat of formation of ethanol from these, and from the heat of combustion that
we measured for it:

,298
(
3

2
()) = 2(393.5) +3(285.8) (1366.7) = 277.7kJ/mol


Reassuringly, this result agrees with the value of standard enthalpy of formation listed for liquid ethanol
in the table in the back of SVA (Table C.4p.686).


The Temperature Dependence of Heats of Reaction:

Now we know how to use heats of formation to compute heats of reaction at a given temperature, but
what if we want to know a heat of reaction at some temperature other than the standard temperature of
25
o
C at which standard heats of formation are generally tabulated? One way that we could compute this
would be to:

(1) compute the enthalpy change for a hypothetical process in which we heat or cool the reactants to the
standard state temperature,

(2) carry out the reaction under standard conditions,

(3) cool or heat the products back to the temperature of interest,

The total enthalpy change for this 3-step process would be equal to the enthalpy change for the 1-step
process of carrying out the reaction at the initial temperature.



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I. For the first step of heating of cooling the reactants to 298.15 K, we have

1
0
=
,

298.15

where
,

is the total heat capacity of the reactants for the reaction as written. For example if
we had the generic reaction

+ +

it would be

() +

()

II. For the second step,carrying out the reaction at 298.15K, we have

2
0
=
,298.15
0


III. Finally, for the 3rd step, bringing the products back to the initial temperature, we have

3
0
=
,

298.15


So, for the overall process, we have

0
=
,
0
=
,

298.15

+
,298.15
0
+
,

298.15


Remembering that switching the limits of an integral (changing the direction of integration) just changes
its sign, we can combine the two integrals to get
ChE 226 2013 Chapter 4
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,
0
=
,298.15
0
+ (
,

298.15



That is ,the heat of reaction at some other temperature is equal to the heat of reaction at the standard
temperature of 298.15 K plus the integral from the standard temperature to the temperature of interest of
the difference in heat capacity between the reactants and the products. just like the enthalpy of reaction is
the difference between the enthalpy of the products and reactants, we can define the change in heat
capacity of reaction as the difference between the total heat capacity of the products and the reactants. So,
for the generic reaction

+ +

for which the heat of reaction is

() +

()

()

()

The difference in heat capacity on reaction would be

() +

()

()

()

where all of the heat capacities can be temperature dependent, so their difference is also temperature
dependent. The heat of reaction at some arbitrary temperature T is then

,
0
=
,298.15
0
+

298.15




We could further generalize this by writing the general chemical reaction with an arbitrary number of
reactants and products as done by SVA on p.137

|
1
|
1
+|
2
|
2
+ |
3
|
3
+|
4
|
4
+

where V
i
is the stoichiometric coefficient of species A
i
(A1, A2, etc.) are just the names of the species
participating in the reaction. The convention we will use here (and that most widely used) is that the
stoichiometric coefficients are positive for products and negative for reactants. Then, the above
equation can be formally written as:

1
+
2

2
+
3

3
+
4

4
+ = 0

or simply

= 0

ChE 226 2013 Chapter 4
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with this notation, the heat of reaction can be written as

0
=

0
(

The change in heat capacity can be written as

and so on. This is very handy for doing things in an automated way on the computer.
If the individual heat capacities of the species are written in the usual polynomial form that we used last
time

2
+

2



Then we can write

2
+

2
)

= + +
2
+
2


where we define

=

; =

Using this notation with the heat capacity integral to find the heat of reaction at some arbitrary
temperature T, we have

,
0
=
,298.15
0
+

298.15

,
0
=
,298.15
0
+ ( + +
2
+
2
)

298.15

,
0
=
,298.15
0
+ ( 298.15 ) +

2
(
2
(298.15 )
2
) +

3
(
3
(298.15 )
3
) (
1

1
298.15
)

As was the case for the usual heat capacity integral, SVA have given a defined function and an example
computer program for this in the appendices of the text.

The final section in chapter 4 of SVA is on Heat Effects of Industrial Reactions. We will study it by
ChE 226 2013 Chapter 4
13


discussing examples from that section. It is based on material developed in this chapter.

Summary
After completing your study of these lecture notes and the associated homework and material from
chapter 4 of SVA, you should be able to:

Compute the standard heat of reaction for a given reaction using tables of heats of formation
Compute heats of formation from heats of combustion
Carry out heat capacity integrals to find a heat of reaction at an arbitrary temperature
Compute heat addition or removal rate (or total) for a specified chemical reaction with specified
inlet and outlet (or initial and final) temperatures
Compute the outlet (or final) temperature for a given chemical reaction and specified inlet (or
initial) temperature and heat addition or removal rate (or total)