Course

CHPE 208: Chemical Engineering

Thermodynamics

Heat Effects

Dr Venkata Ratnam Myneni

Associate Professor
Department of Chemical & Petrochemical Engineering
College of Engineering & Architecture
 Heat Effects
• Heat effects refer to physical and chemical phenomena that
are associated with heat transfer to or from a system or
that result in temperature changes within a system, or
both.
• The temperature changes that occur are known as sensible
heat effects.
• Phase changes, physical processes occurring for a pure
substance at constant temperature and pressure, are
accompanied by latent heats.
• Chemical reactions are characterized by heats of reaction,
which for combustion reactions evolve heat. Every chemical
or biochemical process is associated with one or more heat
effects.
 Sensible Heat Effects
• Heat transfer that results in a change in temperature
of a substance without a change in phase or chemical
composition.
• Governed by the Heat Capacity (C).
– Constant Volume Heat Capacity (CV)​: Defined as the
change in internal energy with respect to temperature at
constant volume:
CV​=(∂T/∂U​)V​
– Constant Pressure Heat Capacity (CP​): Defined as the
change in enthalpy with respect to temperature at
constant pressure:
CP=(∂T∂H​)PP
 Sensible Heat Effects
• Heat Transfer Calculation:
– For a constant pressure process (which is common
for chemical reactors and processes open to the
atmosphere), the heat absorbed or released (Q) is
equal to the change in enthalpy (ΔH):
ΔH=Q​= ∫​​CPdT
– For an ideal gas, CP​ and CV​ are related by:
CP−CV=R
(where R is the universal gas constant)
 Latent Heat Effects
• Heat transfer associated with a change in phase
(e.g., melting, vaporization, sublimation) at a
constant temperature and pressure. This heat
provides the energy needed to overcome
intermolecular forces.
• Key Latent Heats:
– Heat of Fusion (ΔHfusion): Heat required to melt a solid
(solid → liquid).
– Heat of Vaporization (ΔHvap​): Heat required to
vaporize a liquid (liquid → vapor).
– Heat of Sublimation (ΔHsub​): Heat required to sublime
a solid (solid → vapor).
 Heat of Reaction
• The change in enthalpy (ΔH) that accompanies a
chemical reaction at a specified temperature and
pressure. This heat originates from the breaking
and formation of chemical bonds.
• Exothermic Reaction: Releases heat to the
surroundings. ΔH is negative (ΔH<0). Products
have lower enthalpy than reactants.
• Endothermic Reaction: Absorbs heat from the
surroundings. ΔH is positive (ΔH>0). Products
have higher enthalpy than reactants.
Standard Heat of Reaction (ΔHorxn)
• To compare reactions consistently, heat of reaction is often calculated
under standard conditions.
• Standard State: The reference state for a substance at a specified
temperature (T).
– Gas: Pure substance in the ideal gas state at a pressure of 1 bar.
– Liquid or Solid: Pure substance in its real state at a pressure of 1 bar.
• Standard Temperature: While the standard state is pressure-dependent,
reaction data is conventionally tabulated for a standard temperature,
typically 298.15 K (or 25∘C).
 Standard Heat of Formation (ΔHof)
• The enthalpy change when one mole of a
compound is formed from its constituent
elements in their most stable form at the
standard state and a specified temperature
(usually 298.15 K).
• Reference Point: The standard enthalpy of
formation for a pure element in its most stable
form at the standard state is zero by definition
(e.g., ΔHof ​(O2(g)​)=0, ΔHof ​(C(graphite)​)=0).
 STANDARD HEAT OF COMBUSTION
A combustion reaction is defined as a reaction
of an element or compound with oxygen to
form specified combustion products.
The Standard Heat of Combustion, is the
enthalpy change when one mole of a
substance is completely burned in excess
oxygen under standard state conditions.
This process is always exothermic, meaning heat
is released, so the ΔHc∘ value is always
negative.
STANDARD HEAT OF COMBUSTION:
 Hess’s Law of Constant Heat
Summation
• Hess’s Law states:
The total enthalpy change (ΔH) of a chemical
reaction is the same, regardless of the
pathway taken, provided the initial and final
states are the same.

If a reaction can be expressed as a sum of two or more

reactions:
ΔHoverall=ΔH1+ΔH2+ΔH3+……..
 Hess’s Law of Constant Heat
Summation
Key Principles
• Enthalpy depends only on initial and final states, not on
the path.
• Useful when direct measurement of ΔH for a reaction
is difficult.
• Combines known enthalpy changes to calculate
unknown values.
• Hess’s Law validates the additivity of enthalpy changes.
• It is a powerful tool in thermochemistry.
• Practical in cases where direct enthalpy measurement
is not possible.
 Hess’s Law of Constant Heat
Summation
Example 1: Formation of CO₂
We want ΔH for:
C(graphite)+O2(g)→CO2

Pathway 1 (direct):
• Combustion of graphite → CO₂

Pathway 2 (indirect):
Step 1: C + ½ O₂ → CO (ΔH₁ = –110.5 kJ)
Step 2: CO + ½ O₂ → CO₂ (ΔH₂ = –283.0 kJ)

By Hess’s Law:
ΔHoverall = ΔH₁ + ΔH₂ = –110.5 – 283.0 = –393.5 kJ
Heat Effects-Temparature dependency
• A general chemical reaction may be written:

where νi is a stoichiometric coefficient and Ai

stands for a chemical formula.
• The sign convention for νi is as follows:
positive (+) for products and negative (− ) for
reactants
Heat Effects-Temparature dependency
• Standard heat of reaction to be expressed
mathematically by the simple equation:

• where Hi° is the enthalpy of species i in its

standard state and the summation is over all
products and reactants.
Heat Effects-Temparature dependency
• The standard-state enthalpy of a chemical
compound is equal to its heat of formation
plus the standard-state enthalpies of its
constituent elements. If the standard-state
enthalpies of all elements are arbitrarily set
equal to zero as the basis of calculation, then
the standard-state enthalpy of each
compound is simply its heat of formation. In
this event, Hi° = Δ Hfio
Heat Effects-Temparature dependency
• For standard reactions, products and reactants
are always at the standard-state pressure of 1
bar. Standard-state enthalpies are therefore
functions of temperature only

• Multiplying by νi and summing over all

products and reactants gives:
Heat Effects-Temparature dependency
Heat Effects-Temparature dependency
• Calculate the standard heat of the following
methanol-synthesis reaction at 800°C:
CO(g) + 2 H2 (g) → CH3 OH(g)
Heat Effects-Temparature dependency

The value of this integral is −1615.5 K

ΔH° = − 90,135 + 8.314 ( −1615.5 ) = −103,566 J

Heat Effects-Temparature dependency
• Calculate the standard heat of the following
methanol-synthesis reaction at 800°C:
CO(g) + 2 H2 (g) → CH3 OH(g)
Cp at 800oC is 194.31 J/Kg.K

ΔH°= ΔHo°+CPo ΔT
ΔH° = −103,566 J