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Chapter 4:
Heat Effects

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 4.1: Sensible Heat Effects
• Heat transfer to a system in which no phase changes, no
chemical reactions, and no composition changes occur
causes a sensible heat effect: a change in the temperature of
the system.
• According to the Gibbs Phase Rule, for a homogeneous
substance with constant composition, fixing 2 intensive
properties sets the intensive state of the system.
• For internal energy, those two properties are often taken to
be T & V :
𝑈 = 𝑈(𝑇, 𝑉)
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

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 Internal Energy
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

• With the definition of CV from Eqn. (2.15):

𝜕𝑈
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝜕𝑉 𝑇

• The second term is zero for:

– Any closed-system constant-volume process
– A fluid in the ideal gas state
– An incompressible fluid
• In those cases: 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝑇2
∆𝑈 = න 𝐶𝑉 𝑑𝑇 (4.1)
𝑇1
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 Enthalpy 1
• Enthalpy is typically defined in terms of T & P : 𝐻 = 𝐻(𝑇, 𝑃)
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

• With the definition of CP from Eqn. (2.19):

𝜕𝐻
𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑑𝑃
𝜕𝑃 𝑇

• The second term is zero for:

– Any constant-pressure process
– A fluid in the ideal-gas state
• In those cases: 𝑑𝐻 = 𝐶𝑃 𝑑𝑇
𝑇
∆𝐻 = ‫ 𝑇׬‬2 𝐶𝑃 𝑑𝑇 (4.2)
1
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 Enthalpy 2

• Recall, for mechanically reversible, constant-pressure, closed

system processes and for the transfer of heat in steady-flow
processes (where kinetic & potential energy changes are
negligible) where shaft work is 0, Q = ∆H.
• In other words:
𝑇2
𝑄 = ∆𝐻 = න 𝐶𝑃 𝑑𝑇 (4.3)
𝑇1

• This equation is frequently applied in flow process

calculations for simple heating and cooling of gases, liquids,
and solids.

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Temperature Dependence of the Heat Capacity

• Evaluating Eqn. (4.3) requires knowledge of the form of the

heat capacity.
• Various forms are used in various texts - in this text, we use:
𝐶𝑃
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 (4.4)
𝑅
• Depending on the substance, either C or D is usually zero.
• CP/R is dimensionless, so the units of CP are those of R.
• Values of the constants for selected solids and liquids are
given in Tables C.2 and C.3 of Appendix C. Note that those
must be used with T in kelvins.

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 Heat Capacities for Vapors

• For monatomic ideal gases, internal energy corresponds to

only translational kinetic energy, and the heat capacity is:
3 5
𝐶𝑉 = 𝑅 and 𝐶𝑃 = 𝑅
2 2
• For diatomic gases, internal energy includes rotational kinetic
5 7
energy. In this case: 𝐶𝑉 = 𝑅 and 𝐶𝑃 = 𝑅 at low T, and
2 2
heat capacity increases with T as vibration become activated.
• More complex molecules store energy in internal vibrations
and rotations. They have larger heat capacities that increase
with temperature.

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 Heat Capacities for Non-Ideal Vapors
• In general, for the ideal-gas state, we use:
𝑖𝑔
𝐶𝑃
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 (4.5)
𝑅
• Table C.1 has values for A, B, C, and D for many gases
• As is the case for constant heat capacities:
𝑖𝑔 𝑖𝑔
𝐶𝑉 𝐶𝑃
= −1 (4.6)
𝑅 𝑅
• Ideal-gas heat capacities are technically only correct for real
gases in the zero pressure limit; Fig. (3.14) provides guidance
about practical conditions of validity.
• For non-ideal gases, use Eqn. (4.5) with corrections to be
discussed in Chapter 6.
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 Heat Capacities of Mixtures
• In the ideal-gas state, there are no mixture effects, and the
heat capacity is a mole-fraction weighted average:
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
𝐶𝑃,𝑚𝑖𝑥 = ෍ 𝑦𝑖 𝐶𝑃,𝑖 = 𝑦1 𝐶𝑃,1 + 𝑦2 𝐶𝑃,2 +⋯ (4.7)
𝑖

• When combined with Eqn. (4.5):

𝑖𝑔
𝐶𝑃,𝑚𝑖𝑥
= 𝐴𝑚𝑖𝑥 + 𝐵𝑚𝑖𝑥 𝑇 + 𝐶𝑚𝑖𝑥 𝑇 2 + 𝐷𝑚𝑖𝑥 𝑇 −2
𝑅
Where 𝐴𝑚𝑖𝑥 = σ𝑖 𝑦𝑖 𝐴𝑖 , 𝐵𝑚𝑖𝑥 = σ𝑖 𝑦𝑖 𝐵𝑖 , etc.

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 Evaluation of the Sensible-Heat Integral
• Finding ∆H requires evaluation of the heat-capacity integral in
Eqn. (4.2), resulting in:
𝑇
∆𝐻 𝐶𝑃
=න 𝑑𝑇 (4.8)
𝑅 𝑇0 𝑅
𝐵 2 2
𝐶 3 3
𝑇 − 𝑇0
= 𝐴 𝑇 − 𝑇0 + 𝑇 − 𝑇0 + 𝑇 − 𝑇0 + 𝐷
2 3 𝑇𝑇0
• WhenT &T0 are known, evaluation for ∆H is straightforward;
when ∆H and T0 are known, an alternate form is more useful
for finding T :
𝑇
𝐶𝑃
න 𝑑𝑇 =
𝑇0 𝑅
𝐵 𝐶 2 2
𝐷
𝐴 + 𝑇 + 𝑇0 + 𝑇 + 𝑇𝑇0 + 𝑇0 + 𝑇 − 𝑇0
2 3 𝑇𝑇0
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 Sensible-Heat Integral

• We define the quantity in the square brackets as 𝐶𝑃 𝐻 /𝑅.

– The mean heat capacity (for computing ∆H) between T0 and T
𝐶𝑃 𝐻 𝐵 𝐶 2 2
𝐷
≡ 𝐴 + 𝑇 + 𝑇0 + 𝑇 + 𝑇𝑇0 + 𝑇0 + (4.9)
𝑅 2 3 𝑇𝑇0
• Then Eqn. (4.2) becomes: ∆𝐻 = 𝐶𝑃 𝐻 𝑇 − 𝑇0 (4.10)
• Solution for T from Eqn. (4.10) gives:
∆𝐻
𝑇= + 𝑇0 (4.11)
𝐶𝑃 𝐻
• Eqns. (4.9) and (4.11) can be used together to find T iteratively.

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 4.2: Latent Heats of Pure Substances
• When a pure substance changes phase (from vapor to liquid,
liquid to solid, etc.) at constant pressure, no change in
temperature occurs, but a finite amount of heat is transferred
to or from the substance. = latent heat
• For two coexisting phases of a pure substance, Gibbs Phase
Rule tells us that only one intensive property can be
specified, thus the latent heat accompanying a phase change
can be regarded as a function of temperature only.
• The latent heat is related to other system properties by the
Clapeyron equation:
𝑑𝑃 𝑠𝑎𝑡
∆𝐻 = 𝑇∆𝑉 (4.12)
𝑑𝑇

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 Estimating Latent Heats 1
• Latent heats can be measured calorimetrically, or estimated
using correlations like those in Perry’s Chemical Engineer’s
Handbook.
• Heats of vaporization are the most important in practice, and
have received the most attention.
• Rough estimates of the latent heat of vaporization for pure
liquids at their normal boiling point are given by Trouton’s
Rule:
∆𝐻𝑛
~10
𝑅𝑇𝑛
• This is mainly useful as a quick check of the reasonableness of
values from other methods; common values range from 8 for
Ar to 13.1 for H2O.
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 Estimating Latent Heats 2
• At the normal boiling point, the Riedel Equation gives an
estimate of the latent heat as:
∆𝐻𝑛 1.092 ln 𝑃𝑐 − 1.013
= (4.13)
𝑅𝑇𝑛 0.930 − 𝑇𝑟𝑛
where Pc is the critical pressure and 𝑇𝑟𝑛 is the reduced
temperature at Tn
• Eqn. (4.13) is surprisingly accurate – errors rarely exceed 5%
• Estimates of the latent heat of vaporization of a pure liquid at
any temperature relative to a known value can be estimated
using the Watson Equation:
0.38
∆𝐻2 1 − 𝑇𝑟2
= (4.14)
∆𝐻1 1 − 𝑇𝑟1
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 4.3: Standard Heat of Reaction 1
• Chemical reactions are accompanied by the transfer of heat, a
change in temperature, or both – ultimately caused by the
difference in molecular configurations of the products and
reactants.
• Although reactions can occur in very diverse ways, we tabulate
these heat effects for “standard state” processes and
conditions, then modify the results as necessary.
• Standard state – defined as the state of a substance at a specific
pressure, composition, and physical condition.
• Standard states of materials:
– Gases: the pure substance in the ideal-gas state at 1 bar
– Liquids & solids: real, pure substance at 1 bar

• Standard states can be at any temperature.

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 4.3 Standard Heat of Reaction 2
𝑎𝐴 + 𝑏𝐵 → 𝑙𝐿 + 𝑚𝑀
• The standard heat of reaction is defined as the enthalpy
change of the above reaction with reactants and products in
their standard states at the same reference temperature.
• The mechanism of this change is immaterial, effectively
occurring in a “box of tricks”.

Figure 4.2
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 Reaction Stoichiometry

• A general chemical reaction may be written:

𝜈1 𝐴1 + 𝜈2 𝐴2 + ⋯ → 𝜈3 𝐴3 + 𝜈4 𝐴4 + ⋯
Where 𝜈𝑖 is the stoichiometric coefficient, with sign convention:
Positive (+) for products; Negative (-) for reactants
• Example:
𝑁2 + 3𝐻2 → 2𝑁𝐻3
then 𝜈𝑁2 = −1, 𝜈𝐻2 = −3, 𝜈𝑁𝐻3 = +2

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 4.4: Standard Heat of Formation
• Formation reaction – reaction that forms a single compound
from its constituent elements.
• Table C.4 includes a list the standard heats of formation of
many common compounds, evaluated at 25°C.
• For a given reaction, use of the standard heats of formation
and reaction stoichiometry allows calculation of the standard
heat of reaction for any real reaction.
𝑜 𝑜
∆𝐻298 = ෍ 𝜈𝑖 ∆𝐻𝑓,298

𝑜 𝑜
= ෍ 𝜈𝑖 ∆𝐻𝑓,298 − ෍ 𝜈𝑖 ∆𝐻𝑓,298
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

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 Example 4.5

Calculate the standard heat of reaction at 25°C for the

following reaction:
4𝐻𝐶𝑙 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔 + 2𝐶𝑙2 (𝑔)

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 4.5: Standard Heat of Combustion
• Combustion reaction – reaction of an element or compound
with oxygen to form specified combustion products.
• For organic compounds containing only C, H, and O, the products
are only CO2 and H2O, but the water can be liquid or vapor.
• Heats of formation are often obtained from heats of
combustion, measured calorimetrically.
• Data are always based on 1 mol of the substance burned.
• Like calculations with standard heats of formation:
𝑜 𝑜 𝑜 𝑜
∆𝐻298 = ෍ 𝜈𝑖 ∆𝐻𝑐,298 = ෍ 𝜈𝑖 ∆𝐻𝑐,298 − ෍ 𝜈𝑖 ∆𝐻𝑐,298
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

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 4.6: Temperature Dependence of ΔH °1
• The previous calculations provide the standard heat of
reaction at 25°C.
• Back to the general chemical reaction:
𝜈1 𝐴1 + 𝜈2 𝐴2 + ⋯ → 𝜈3 𝐴3 + 𝜈4 𝐴4 + ⋯
• As noted before, the standard heat of reaction can be
expressed mathematically:

∆𝐻 𝑜 ≡ ෍ 𝜈𝑖 𝐻𝑖𝑜 (4.15)

• If the enthalpies of formation of the elements in their

standard states are set equal to zero, then the enthalpy of
each compound is its enthalpy of formation, and:
𝑜
∆𝐻 𝑜 = σ 𝜈𝑖 ∆𝐻𝑓,𝑖 (4.16)
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 4.6: Temperature Dependence of ΔH° 2
• At standard state, P = 1 bar, and standard-state enthalpies are
functions of temperature only:
𝑑𝐻𝑖𝑜 = 𝐶𝑃𝑖
𝑜
𝑑𝑇 (2.20)
• Multiplying by stoichiometric coefficients & summing over all
species:
෍ 𝜈𝑖 𝑑𝐻𝑖𝑜 = ෍ 𝜈𝑖 𝐶𝑃𝑖
𝑜
𝑑𝑇
𝑖 𝑖

෍ 𝑑 𝜈𝑖 𝐻𝑖𝑜 = ෍ 𝜈𝑖 𝐶𝑃𝑖
𝑜
𝑑𝑇
𝑖 𝑖

• The term in the parenthesis is ∆H °(4.15) and defining:

𝑜
∆𝐶𝑃𝑜 ≡ σ𝑖 𝜈𝑖 𝐶𝑃𝑖 (4.17)
• Thus: 𝑑∆𝐻 𝑜 = ∆𝐶𝑃𝑜 𝑑𝑇 (4.18)
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 4.6: Temperature Dependence of ΔH° 3

𝑑∆𝐻 𝑜 = ∆𝐶𝑃𝑜 𝑑𝑇 (4.18)

• Integration yields the relationship between heat of reaction
and temperature:
𝑇
∆𝐻 𝑜 − ∆𝐻0𝑜 = න ∆𝐶𝑃𝑜 𝑑𝑇
𝑇0

• ∆𝐻𝑜 𝑎𝑛𝑑 ∆𝐻0𝑜 are the standard heats of reaction at temperature T and
at reference temperature T0, respectively.

• This equation is more conveniently expressed as:

𝑇𝑜
∆𝐶𝑃
∆𝐻 𝑜 = ∆𝐻0𝑜 + 𝑅 න 𝑑𝑇 (4.19)
𝑇0 𝑅

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 4.6: Temperature Dependence of ΔH° 4
𝑇 𝑜
∆𝐶𝑃
∆𝐻 𝑜 = ∆𝐻0𝑜 + 𝑅 න 𝑑𝑇 (4.19)
𝑇0 𝑅

• By use of the analog to Eqn. (4.8), the integral becomes

∆𝐶𝑃𝑜
𝑇
න 𝑑𝑇 (4.20)
𝑇0 𝑅
∆𝐵 2 2
∆𝐶 3 3
𝑇 − 𝑇0
= ∆𝐴 𝑇 − 𝑇0 + 𝑇 − 𝑇0 + 𝑇 − 𝑇0 + ∆𝐷
2 3 𝑇𝑇0
Where by definition: ∆𝐴 ≡ σ 𝜈𝑖 𝐴𝑖 , and so on for ∆B, ∆C, & ∆D
• By analogy with Eqn. (4.9), using ∆CP , (4.19) becomes:
∆𝐻 𝑜 = ∆𝐻0𝑜 + ∆𝐶𝑃𝑜 𝐻 𝑇 − 𝑇0 (4.22)

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 Figure 4.3: Standard Heat of Reaction at any T

Figure 4.3

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 Example 4.6

Calculate the standard heat of the following methanol-

synthesis reaction at 800°C:
𝐶𝑂 𝑔 + 2𝐻2 (𝑔) → 𝐶𝐻3 𝑂𝐻(𝑔)

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 4.7: Heat Effects of Industrial Reactions
• While the preceding sections dealt with the standard heat of
reaction, industrial reactions are rarely carried out under
standard-state conditions.
• Often, reactants are not present in stoichiometric
proportions, or the reaction does not go to completion, or the
inlet and outlet temperatures differ.
• Also, inert substances may be present, and several reactions
may occur simultaneously.
• Nevertheless, calculations are based on the principles laid out
in this chapter.
• Here, we assume the ideal-gas state for all gases.

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 Example 4.8: Multiple Reactions
One method for the manufacture of “synthesis gas” (a mixture of
CO and H2) is the catalytic reforming of CH4 with steam at high
temperature at atmospheric pressure:
𝐶𝐻4 𝑔 + 𝐻2 𝑂 𝑔 → 𝐶𝑂 𝑔 + 3𝐻2 (𝑔)
The only other reaction considered here is the water-gas-shift
reaction:
𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 → 𝐶𝑂2 𝑔 + 𝐻2 (𝑔)
Reactants are supplied in the ratio of 2 mol steam to 1 mol CH4,
and heat is added to the reactor to bring the products to a
temperature of 1300 K. The CH4 is completely converted, and the
product stream contains 17.4 mol-% CO. Assuming the reactants
to be preheated to 600 K, calculate the heat requirement for the
reactor.
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 Example 4.8: Solving…
Defining ∆𝐻𝑅𝑜 as the heat to cool the reactants from 600 K,
𝑜
∆𝐻298 as the heat of reaction at 25°C, and ∆𝐻𝑃𝑜 as the heat of
heating the products to 1300 K

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