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Chapter 4 - (ChE 103 - Heat Effects)

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18 views19 pages

Chapter 4 - (ChE 103 - Heat Effects)

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dark.knight5027
Copyright
© © All Rights Reserved
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ChE 103:

Engineering
Thermodynamics

Course Teacher:
Dr. Nahid Sanzida
Chapter 4
Heat Effects

Scope of this Chapter:


• Sensible heat effects, characterized by temperature changes
• Heat capacities as a function of temperature and their use through defined
functions
• Heats of phase transition, i.e., latent heats of pure substances
• Heats of reaction, combustion, and formation
• Heats of reaction as a function of temperature
• The calculation of heat effects for industrial reactions
4.1 Sensible Heat Effects:
Heat transfer to or from a system in which there are no phase transitions, no chemical reactions, and
no changes in composition causes a sensible heat effect, i.e., the temperature of the system is caused
to change.
• For any closed-system constant-volume process, for a unit mass or a mole
Valid for,
▪ any closed-system constant-volume process.
▪ Whenever the internal energy is independent of
volume, as for the ideal-gas state and the
incompressible liquid.

• For any constant-pressure process, for a unit mass or a mole


Valid for,
▪ any constant-pressure process.
▪ when the enthalpy is independent of pressure,
regardless of process. This is exactly true
for the ideal-gas state and approximately true
for real gases at low pressure and high
temperature.
Temperature Dependence of the Heat Capacity:
The relation between the two temperature scales is:
T (K) = t (°C) + 273.15 .
4.2 LATENT HEATS OF PURE SUBSTANCES:
The latent heat accompanying a phase change is a function of temperature only, and is related to other system
properties by an exact thermodynamic equation:
Table B.1: Characteristic Properties of Pure Species
4.3 STANDARD HEAT OF REACTION:
The heat of reaction, ΔHr =(T, P), is the enthalpy difference when stoichiometric quantities of reactants at
a specified temperature and pressure react completely and the products are at the same temperature and
pressure.

With respect to the


chemical reaction,
aA + bB → lL + mM

The standard heat of reaction, ∆𝐻𝑟𝑜 , is the heat of


reaction when both the reactants and products
are at a specified reference temperature and
pressure, usually (and always in our calculations)
25°C and 1 atm.

CH4(g) + H2O(g) → CO(g) + 3H2(g) ∆𝐻𝑟𝑜 = 205,813 J


CO(g) + H2O(g) → CO2 (g) + H2(g) ∆𝐻𝑟𝑜 = −41,166 J
Chapter 9 of Felder book
4.4 STANDARD HEAT OF FORMATION:
A formation reaction of a compound is the reaction in which the compound is formed from its
elemental constituents as they normally occur in nature (e.g., O2 rather than O).

M The enthalpy change associated with the formation of 1 mole of the compound at a reference
temperature and pressure (usually 25°C and 1 atm) is the standard heat of formation of the
compound, ∆𝐻𝑓𝑜
STANDARD HEAT OF REACTION FROM STANDARD HEAT OF FORMATION:
∆𝐻𝑟𝑜 =?

You should be able to convince yourself that

As we assumed formation positive so, deformation must be negative.

Clear
4.5 STANDARD HEAT OF COMBUSTION:

M The standard heat of combustion of a substance, ∆𝐻𝑐𝑜, is the heat of the combustion of that
substance with oxygen to yield specified products [e.g., CO2(g) and H2O(l)], with both reactants and
products at 25°C and 1 atm (the arbitrary but conventional reference state).
4.6 TEMPERATURE DEPENDENCE OF ΔH°:
The process path that leads to this expression for (recalling
that the reference states are the reactants and products at
25oC and 1 atm) is

The extent of reaction () is a quantity


that measures the extent in which the
reaction proceeds.

Writing H = H 1 + H 2 + H 3 and substituting for each of the
three enthalpy changes on the right leads to the given
expression for H .

The extent of reaction is clearly dimensionless


TEMPERATURE DEPENDENCE OF ΔH°: Use the following formula instead

Look at Table C.4 in


APPENDIX C. Heat Capacities and
Property Changes of Formation

Look at Table C.1, C.2, C.3 in


APPENDIX C. Heat Capacities and
Property Changes of Formation
A process for the production of 1,3-butadiene results from the catalytic dehydrogenation at atmospheric pressure of 1-
butene according to the reaction: C4 H8 (g) → C4 H6 (g) + H2 (g)
To suppress side reactions, the 1-butene feed stream is diluted with steam in the ratio of 10 moles of steam per mole of 1-
butene. The reaction is carried out isothermally at 525°C, and at this temperature 33% of the 1-butene is converted to 1,3-
butadiene. How much heat is transferred to or from the reactor per mole of entering 1-butene?
Solution

Do yourself by using
HEAT EFFECTS OF INDUSTRIAL REACTIONS:

Because the maximum attainable temperature (called the theoretical flame temperature) is sought,
assume that the combustion reaction goes to completion adiabatically (Q = 0). If the kinetic- and
potential-energy changes are negligible and if Ws = 0, the overall energy balance for the process
reduces to ΔH = 0.
A fuel consisting of 75 mol-% methane and 25 mol-% ethane enters a furnace with 80% excess air at 30°C. If 8 × 105
kJ·kmol-1 fuel is transferred as heat to boiler tubes, at what temperature does the flue gas leave the furnace? Assume
complete combustion of the fuel.

Do yourself by using

Example 9.5-1 Example 9.5-3


Synopsis:

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