CHG 2324
Fundamentals and applications of chemical
engineering thermodynamics
Chapter 4
Winter 2025
Prof. Andrew Anstey
Department of Chemical and Biological Engineering
University of Ottawa 1
Outline
Key ideas in this chapter:
• Sensible heat effects
• Temperature dependence of thermodynamic properties
• Enthalpy of chemical processes
→ Enthalpy of phase transitions
→ Enthalpy of reaction
→ Enthalpy of formation
→ Enthalpy of combustion
→ Temperature dependence of enthalpy
• Thermal effects in industrial reactions
2
Sensible heat effects
Sensible heat is the amount of heat needed to change the temperature of a
system in the absence of any phase transitions, chemical reactions, or other
change in the composition of the system.
For a system composed of a single substance with uniform composition, Gibbs’
phase rule indicates that it can be fully described with two intensive properties. We
can express the internal energy of such a system as U = U(T, V):
𝑽 𝑻
3
Sensible heat effects
Incorporating equation 2.15, we can express this as:
𝑽
𝑻
The second term reduces to zero for:
→ Any closed, constant volume process: dV = 0
𝝏𝑼
→ Any fluid in the ideal-gas state: =0
𝝏𝑽
→ An incompressible fluid: dV = 0
𝑻𝟐
𝑽 𝑻𝟏 𝑽 4.1
4
Sensible heat effects
Enthalpy is handled similarly, and can be defined as H = H(T, P) :
𝑷
𝑷 𝑻 𝑻
The second term reduces to zero for:
→ Any closed, constant pressure process: dP = 0
𝝏𝑯
→ Any fluid in the ideal-gas state: =0
𝝏𝑷
𝑻𝟐
𝑷 𝑻𝟏 𝑷 4.2
5
Sensible heat effects
Recall that for:
→ mechanically reversible, constant-pressure, closed processes
→ Heat transfer in steady-flow processes for which 𝑺
𝑻𝟐
𝑷 4.3
𝑻𝟏
This equation is commonly used in flow processes for simple heating and cooling
(ie; heat exchangers).
6
Sensible heat effects
To use equation 4.3 across a range of temperatures, we need to be able to
evaluate the temperature dependence of the heat capacity. Empirical equation:
𝑷 𝟐 𝟐 4.4
• C and D are usually zero, depending on the substance.
• 𝑷 is dimensionless.
• Values for constants are given in Appendix C.1-C.3
7
Sensible heat effects
A homogeneous mixture of gases can be treated as a pure gas. In the ideal-gas
state, there are no mixture effects, and the heat capacity can be determined via the
mole-fraction weighted average:
, , , , , 4.7
𝒊𝒈
where i is the number of components in the mixture, and 𝒊 and 𝑷,𝒊 are the molar
fraction and specific heat capacity in the ideal-gas state of the ith component,
respectively.
8
Sensible heat effects
To determine enthalpy of a sensible heat effect, we evaluate equation 4.2 and
substitute 4.5 for the value of 𝑷 .
𝑻
𝑷 𝟐 𝟐 𝟑 𝟑 𝟎
𝟎 𝟎 𝟎 4.8
𝑻𝟎 𝟎
For known T and T0, the evaluation of is straightforward. In cases where T0 and
are known, we can refactor 4.8 to a more useful form to determine T:
𝑻
𝑷 𝟐 𝟐
𝟎 𝟎 𝟎 𝟎
𝑻𝟎 𝟎
9
Sensible heat effects
From equation 4.8, we define a mean heat capacity 𝑷 𝑯 for the temperature
range between T0 and T, where 𝑷 𝑯 is equivalent to the terms inside the
square brackets of equation 4.8:
𝑷 𝑯 𝟐 𝟐
𝟎 𝟎 𝟎 4.9
𝟎
Equation 4.2 can then be rewritten as follows and used to solve iteratively for T
(see text p.143 for details on iteration approach):
𝑷 𝑯 𝟎 4.10
𝟎 4.11
𝑷 𝑯
10
Latent heats of pure substances
When a pure substance changes phase at constant pressure, there is no
temperature change across the phase transition, although there is a transfer of
heat. This type of heat effect is known as a latent heat, described by the
Claperyon equation:
𝒔𝒂𝒕
4.12
where is the latent heat (or enthalpy) of transition, is the volume
𝒅𝑷
accompanying the phase change, and 𝒔𝒂𝒕 is the slope of the saturation curve on a
𝒅𝑻
P-T diagram.
11
Latent heats of pure substances
Latent heats can be measured via calorimetry, or estimated using correlations
found in literature. Rough estimates for the heat of vaporization for pure liquids at
their normal boiling point (ie; at atmospheric pressure) are given by Trouton’s rule:
𝒏
𝒏
12
Latent heats of pure substances
More accurate estimates for latent heat at the normal boiling point Tn can be given
by the Riedel equation:
𝒏 𝑪
4.13
𝒏 𝒓𝒏
where Pc is the critical pressure (in bar), and Trn is the reduced temperature at Tn .
The latent heat of vaporization of a pure liquid at any temperature relative to a
known value can be estimated using the Watson equation:
.
4.14
13
Example 4.4: Given that the latent heat of vaporization of water at 100°C is 2257
J/g, estimate the latent heat at 300°C.
14
Standard heat of reaction
Chemical reactions are accompanied by a transfer of heat, change in temperature,
or both. These arise due to the change in molecular configurations of the reactants
and products during the reaction.
The heat of reaction, or the reaction enthalpy, is used to measure these effects.
Using this quantity effectively requires us to specify:
→ The temperature at which the reaction is happening
→ The composition/amount of the reactants and products
→ The physical state of the reactants and products
The standard heat of reaction refers to the enthalpy change of the reaction at
standard conditions. Standard states are generally defined as:
→ Gases: the pure substance in the ideal-gas state at 1 bar.
→ Liquids and solids: the pure liquid or solid at 1 bar. 15
Standard heat of reaction
If the properties of the reactants and products in their standard states are not
significantly different from the properties of the actual reactants and products, the
standard heat of reaction provides a reasonable approximation of the actual heat
of reaction. Standard states are functions of temperature only.
16
Image via Smith and Van Ness, 9th edition
Standard heat of reaction
The general equation for a chemical reaction is given as:
𝟏 𝟏 𝟐 𝟐 𝟑 𝟑 𝟒 𝟒
where vi is the stoichiometric coefficient. The sign convention is positive for
products and negative for reactants.
For: 𝟐 𝟐 𝟑
𝑵𝟐 𝑯𝟐 𝑵𝑯𝟑
17
Standard heat of formation
By definition, the standard heat of formation °𝒇𝑻 at temperature T is the standard
heat of a reaction that forms a single product from its constituent elements. Values
for °𝒇𝑻 can be found in Appendix C.4.
° ° ° °
, , , ,
18
Standard heat of formation
Consider the reaction of CO2 (g) + H2 (g) → CO (g) + H2O (g) at 25 °C:
°
CO2 (g): C(s) + O2(g) → CO2 (g) 𝒇𝟐𝟗𝟖 = -393.5 kJ
°
H2 (g): 𝒇𝟐𝟗𝟖 = 0 kJ
°
CO (g): C(s) + ½ O2(g) → CO (g) 𝒇𝟐𝟗𝟖 = -110.5 kJ
°
H2O (g): H2(g) + ½ O2(g) → H2O (g) 𝒇𝟐𝟗𝟖 = -241.8 kJ
Then:
°
CO2 (g) → C(s) + O2(g) 𝒇𝟐𝟗𝟖 = 393.5 kJ
°
C(s) + ½ O2(g) → CO (g) 𝒇𝟐𝟗𝟖 = -110.5 kJ
°
H2(g) + ½ O2(g) → H2O (g) 𝒇𝟐𝟗𝟖 = -241.8 kJ
°
CO2 (g) + H2 (g) → CO(g) + H2O (g) 𝒇𝟐𝟗𝟖 = 41.2 kJ
19
Standard heat of formation
Imagine for the same reaction, we were only provided with the heat of formation for
water in the liquid state at 25 °C. From C.4, for H2O (l), °𝒇𝟐𝟗𝟖 = -285.3 kJ.
We must modify our calculation to account for the enthalpy of the phase change,
but ultimately we will end up with the same result:
°
CO2 (g) → C(s) + O2(g) 𝒇𝟐𝟗𝟖 = 393.5 kJ
°
C(s) + ½ O2(g) → CO (g) 𝒇𝟐𝟗𝟖 = -110.5 kJ
°
H2(g) + ½ O2(g) → H2O (l) 𝒇𝟐𝟗𝟖 = -285.3 kJ
°
H2O (l) → H2O (g) 𝒇𝟐𝟗𝟖 = 44.0 kJ
°
CO2 (g) + H2 (g) → CO2(g) + H2O (g) 𝒇𝟐𝟗𝟖 = 41.2 kJ
20
Standard heat of combustion
Combustion reactions refer to the reaction of an element of compound with oxygen
°
to form combustion products. Standard heats of combustion , are relatively
easy to measure experimentally using a calorimeter, and can be used to determine
heat of reaction for more complex pathways that are difficult to evaluate
experimentally.
° ° ° °
, , , ,
21
Standard heat of combustion
For the formation of n-butane, we can determine the heat of formation by
combining 3 separate combustion reactions:
4C (s) + 5 H2(g) → C4H10(g)
°
4C(s) + 4O2(g) → 4CO2 𝒇𝟐𝟗𝟖 = (4)(-393.5 kJ)
°
5H2(g) + 2½ O2(g) → 5H2O (l) 𝒇𝟐𝟗𝟖 = (5)(-285.3 kJ)
°
4CO2 + 5H2O (l) → C4H10(g) + 6½ O2(g) 𝒇𝟐𝟗𝟖 = 2,877.4 kJ
°
4C (s) + 5 H2(g) → C4H10(g) 𝒇𝟐𝟗𝟖 = -125.8 kJ
22
Temperature dependence of ΔH°
We can define the standard heat of reaction as:
° °
𝒊 𝒊 4.15
If the enthalpies of formation of the elements in their standard states are equal to
zero, then the enthalpy of each component in a reaction is equal to its enthalpy of
formation, and equation 4.15 becomes:
° °
𝒊 𝒇,𝒊 4.16
For example, for the reaction 4HCl (g) + O2 (g) → 2H2O (g) + 2Cl2 (g):
° ° °
𝒇𝑯𝟐𝑶 𝒇𝑯𝑪𝒍
23
Temperature dependence of ΔH°
Enthalpy is related to temperature at standard conditions (P = 1 bar) by:
° °
𝑷 4.18
Integrating 4.18 gives us:
𝑻
° ° °
𝟎 𝑷
𝑻𝟎
° °
where and 𝟎 are the standard heats of reaction at temperature T and
temperature T0, respectively. For the standard reference temperature of 25 °C:
𝑻
°
° ° 𝑷
𝟎 4.19
𝟐𝟗𝟖.𝟏𝟓
24
Temperature dependence of ΔH°
Equation 4.19 can be expanded in similar fashion to 4.8 using an empirical
equation to produce:
𝑻 °
𝑷 𝟑 𝟎
𝟎
𝟐 𝟐
𝟎
𝟑
𝟎 4.20
𝑻𝟎 𝟎
where 𝒊 𝒊 𝒊 𝒊 etc…
So then similarly to eq 4.10, eq 4.19 becomes:
° ° ° 4.22
𝒓 𝟎 𝑷 𝑯 𝟎
25
Temperature dependence of ΔH°
To illustrate how we use equation 4.19 – 4.22 in practice:
26
Image via Smith and Van Ness, 9th edition
Heat effects of industrial reactions
While this chapter dealt with the standard heat of reaction, industrial reactions are
rarely carried out under standard-state conditions.
→ Reactants and products rarely in standard state
→ Reactants may not be present in stoichiometric proportions
→ Reaction may not proceed to completion
→ Temperature gradients may exist in the reactor
→ Inert species may be present
→ Multiple reaction routes are possible, and may be in competition with each
other
27
Image via Smith and Van Ness, 9th edition
Example 4.7: What is the maximum temperature that can be reached by the
combustion of methane with 20% excess of air? Both methane and air enter the
burner at 25°C.
Use appendix C.4 to find heats of formation.
28
Image via Smith and Van Ness, 9th edition
Next lecture: Chapter 5
Reading: Chapter 4, Chapter 5.1-5.5
Practice problems:
Example problems 4.3, 4.6, 4.8
Practice problems 4.1, 4.5, 4.8, 4.12, 4.16, 4.19, 4.22, 4.23
(a,c,f,k,r,w), 4.33, 4.36, 4.42, 4.49
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