CTDCHA2: Chemical Thermodynamics 2A

LEARNING UNIT 3

Heat Effects

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Heat Effects
• Heat transfer is one of the most common operations in the
chemical industry.
• Design of reactors requires knowledge of the rate of heat transfer
(and this depends on heat effects associated with chemical
reactions).
• Sensible heat effects are characterised by temperature
changes only i.e. there are no phase transitions, chemical
reactions or changes in composition.
• Heat effects of chemical reactions, phase transition, formation
and separation of solutions are determined from experimental
measurements (which are made at constant temperature).
• In this learning unit, we apply thermodynamics to evaluate most
of the heat effects that accompany physical and chemical
operations.

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 Heat Effects
The heat effects to be considered in this module are:

• Sensible heat effects which are characterised by changes in

temperature

• Heats of reaction from chemical reactions

• Phase changes (addition or withdrawal of heat does not produce a

temperature change)-latent heats of pure substances

• Heats of formation (when a compound is formed from its

constituent elements)

• Heat capacities as a function of temperature and their use through

defined functions

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Sensible Heat Effects

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Sensible Heat Effects (cont.)

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Sensible Heat Effects (cont.)

and high temperatures

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Sensible Heat Effects (cont.)

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Sensible Heat Effects (cont.)

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Example

Click here for solution

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Solving heat capacity equation

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Solving heat capacity equation (cont.)

⟨ 𝐶 𝑃 ⟩ 𝐻
𝑅

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Example

Calculate the heat required to raise the temperature of 1 mol

of methane from 533.15 to 873.15K (260 to 600oC) in a
steady-flow process at a pressure sufficiently low that
methane may be considered an ideal gas. Use A = 1.702; B =
9.081x10-3; C = -2.164x10-6; D = 0 (from Appendix C for
methane)
Click here for solution

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Example

What is the final temperature when heat in the amount

of 422 MJ is added to 11.3 kmol of ammonia initially
at 533.15 K (260oC) in a steady-flow process at ~1
atm?

Click here for procedure to follow and solution

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Heat Capacities of Gas Mixtures

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Latent Heat(s) of Pure Substances
• These are changes in heat energy accompanied by change of a
substance from one phase to another (at constant temperature).
• Latent heat(s) of phase changes are for physical processes only.

Change from Change to Latent heat of Latent heat of

reverse process

Solid Liquid Melting Freezing/Fusion

Liquid Gas Vaporisation Condensation
Solid Gas Sublimation Sublimation?

• During this process there is co-existence of two phases of a single

species which (according to the phase rule) is univariant.
• The intensive state is determined by the specification of just one
intensive property (T or P or V).

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Latent Heat(s) of Pure Substances
(cont.)

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Estimate of the Latent Heat of
Vaporisation of a Pure Substance

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Example

Click here for solution

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Standard Heat/ Enthalpy of
Reaction
• Chemical reactions are accompanied either by transfer of heat or by T
changes during the course of reaction and in some cases by both.
• This is due to differences in molecular structure and in energy of products
and reactants.
• Calculation of all possible heat changes for all possible reactions is
impossible as heat released or absorbed differs with conditions.
• Calculation of heat effects for reactions is done at standard conditions
and can be applied to reactions occurring at other conditions.
• General reaction: aA + bB  cC+dD ; heat is released or absorbed by the
reaction.
• If the reaction occurs at standard states of T (of 298.15K) and P (of 1 bar),
the heat change is called standard heat of reaction, Hrxno

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Standard Heat/ Enthalpy of
Reaction
• Standard heat (enthalpy) of reaction is defined as enthalpy change when a
moles of A and b moles of B in their standard states at temperature T react to
form c moles of C and d moles of D in their standard states at the same
temperature T.
• Table C.1 for Cp values applies as data was obtained under standard
conditions.
• When Hrxno is given for a particular reaction, it applies for the stoichiometric
coefficients given. If each stoichiometric coefficient is doubled, the heat of
reaction should be doubled.
• When a reaction releases heat to the surroundings it is an EXOTHERMIC
reaction and enthalpy of reaction is negative.
• When a reaction absorbs heat from the surroundings, it is an ENDOTHERMIC
reaction and enthalpy of reaction is positive.
• Enthalpy of reaction is given special names when different processes occur
e.g. enthalpy of combustion when a fuel burns in oxygen to give CO 2/CO and
H2O.
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Example

Click here for solution

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Standard Heat/ Enthalpy of
Formation
• When chemical equations are
combined by addition, the standard
heats of reaction must be added to
give the standard heat of the
resulting reaction (enthalpy
changes are independent of path).
• Tables of heats of formation for
common substances are in standard
handbooks while an abridged list of
values is given in
Table C.4 of Appendix C.
• These can be used to calculate
heats of reaction for any chemical
reaction at any other temperature.

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Example

Click here for solution

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Calculation of Enthalpy of Reaction

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Enthalpy of Combustion

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Calculating Hrxn at Temperatures
that are not 298.15K

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Example

Click here for solution

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Heat Effects of Industrial Processes
Industrial processes have many difficulties:
1. They do not occur at standard T of 298K
2. Reactants may not be present in stoichiometric
proportions
3. Reaction may not go to completion
4. Final T will be different from initial T
5. Inert species may be present reducing yield
and conversion efficiencies
6. Several reactions may occur simultaneously
However, most industrial reactions involve combustion
reactions

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Heat Effects of Industrial
Processes (cont.)

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Heat Effects of Industrial
Processes (cont.)

HrxnT

Hreactantso Hproductso

Hrxno
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Combustion Process
• Air entering a combustion chamber normally
contains some water vapour
• For most combustion processes, water vapour in air
and H2O that forms during combustion can also be
treated as an inert gas, like N 2
• During combustion, O2 is brought into contact with
fuel
• But fuel must be brought above its ignition
temperature (Tig) to start the combustion

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Combustion Process (cont.)

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Combustion Process (cont.)
• Incomplete combustion is when the combustion products contain any
unburned fuel or components such as C, H2, CO, or OH.
• Incomplete combustion is due to:
1. Insufficient O2
2. Presence of more O2 in combustion chamber than is needed for complete combustion.
This may be attributed to insufficient mixing in the combustion chamber during limited
time that the fuel and O2 are in contact
3. Dissociation which becomes important at high T
4. Reaction of O2 with H2 first before reacting with C  H2 in fuel normally burns to
completion, forming H2O, even when there is less O2 than needed for complete
combustion. Some of the C ends up as CO or just as plain C particles (soot) in the
products

• Minimum amount of air needed for complete combustion of a fuel is called

stoichiometric or theoretical air.
• When a fuel is completely burned with theoretical air, no uncombined O2 is
present in the product gases.

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Combustion Process (cont.)

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Example
A boiler is fired with a high-grade fuel (C11.6H17) oil (consisting only of
hydrocarbons) having a standard heat of combustion of -43515 J/g at
298.15 K (25 oC) with CO2(g) and H2O(l) as products.

• The temperature of the fuel and air entering the combustion

chamber is 298.15K.
• The air is assumed dry.
• The flue gases leave at 573.15 K (300 oC) and their average
analysis (on a dry basis) is 11.2% CO2, 0.4% CO, 6.2% O2
and 82.2% N2.
Calculate the fraction of heat of combustion of oil that is
transferred as heat to the boiler.
Click here for solution

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 For this course, the prescribed/ recommended textbook is:

“Introduction to Chemical Engineering Thermodynamics”. Smith and Van Ness,

6th / 7th Edition, McGraw-Hill.

For additional reference/ reading you can

consult the following book/s (as necessary):
• “Chemical and Process Thermodynamics”. Kyle, 3rd Edition, Prentice
Hall International Series.
• “Chemical, Biochemical and Engineering Thermodynamics”.
Sandler, 4th Edition, John Wiley and Sons, Inc.
• “Schaum’s Outline of Theory and Principles of Thermodynamics”.
Abbott and Van Ness, 2nd Edition, McGraw-Hill.
• “Understanding Engineering Thermodynamics”. Levenspiel, Prentice
Hall PTR.
• “Thermodynamics and its Applications”. Tester and Modell, 3rd
Edition, Prentice Hall.

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Homework - read Chapter 4 in the textbook:
Smith, J.M., Van Ness, H.C., Abbott , M.M. (2005), Introduction to
Chemical Engineering Thermodynamics. 7th Edition, McGraw-Hil

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