Chapter 4: Heat-Effects

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 Heat Effects

Physical and chemical phenomena associated with heat transfer 

 Temperature change ….. Sensible Heat

 Phase change (vaporization, fusion, sublimation) …..Latent Heat

 Chemical reaction, separation, mixing, Industrial Reaction …..Enthalpy/Heat of Reaction

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Summary_Heat Effects

 Heat added/removed (Q or ΔH @ const P) ~ Phase change (separation)

 Heat added/removed (Q or ΔH @ const P) ~ Temperature change (heating or cooling)

 Heat added/removed (Q or ΔH @ const P) ~ Reactions, mixing, separation

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Sensible Heat Vs Latent Heat

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5
2 CHE F213 Chemical Engineering Thermodynamics

5
S DOF for a Homogeneous Systems
e
p
t
e
m “When the system is a “Homogeneous Substance” of constant composition, the
b
e phase rule indicates that fixing the values of “two intensive propertie”
r establishes its TD state”
2
0
2
5  “Molar or specific internal energy (U)” may be expressed as a function of temperature and
molar/specific volume.

 “Molar or specific enthalpy (H)” may be expressed as a function of temperature and pressure

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6 CHE F213 Chemical Engineering Thermodynamics
2
5
SHeat Capacities
e
p
t
e
m
b
e
r
2 “Most of the chemical reactions occur at
constant pressure,
0  For any closed-system constant-volume process.
so enthalpy
 For any is more oftenprocess
constant-pressure
2
 Whenever the internal energy isused to measure
independent of volume heats
 of reaction
When than
the enthalpy is independent of pressure (true for
5 the ideal-gas state and approximately true for real gases
internal energy”
(true for ideal-gas state and the incompressible liquid)
at low P high T
When second term is zero; Ideal Case When second term is zero; Ideal case

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Heat Capacity Vs Temperature

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Sensible-Heat Integral

“For solving unknown final temperature, the Mean-Heat Capacity Equation will be used”

Defined Integral Functions Defined mean Functions

integral value specific to enthalpy calculations mean value specific to enthalpy calculations

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Problem Statement: Sensible Heat

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Problem Statement: Sensible Heat

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Problem Statement: Sensible Heat

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Latent heat of Pure Substances

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Application of Clapeyron’s Equation

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2
1 CHE F213 Chemical Engineering Thermodynamics

4
5
Estimating Latent Heats
S
e
p
t
e Trouton’s rule: Rough estimates of latent heats of vaporization for pure liquids at
m their normal boiling points (Tn)
b
e
r Riedel Rule:
2
0
H n 1.092(ln PC  1.013)
2 
5 RTn 0.930  Trn
Watson Rule:

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Problem Statement: Latent Heat

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Problem Statement: Latent Heat

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Temperature Dependence of ΔH°

Standard heat of reaction

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Enthalpy Calculations: Heat of Reaction

IDCPH(T0, T; DA, DB, DC, DD)

MDCPH(T0, T; DA, DB, DC, DD)

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Problem Statement: Heat of Formation

Standard State-condition

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Problem Statement: Heat Effects due to Temperature Change

Non-Standard State-condition

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Chapter 5: Second Law of
Thermodynamics

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 Chapter Outline

 Statements of the Second Law (“Direction of Heat Flow & Entropy”)

 Entropy
 Heat Engines & Carnot Engine
 Entropy changes for the Ideal-Gas State.
 Entropy Balance for Open Systems
 Calculation of Ideal Work & Lost Work (“Irreversibilities”)
 Third Law of Thermodynamics
 Entropy from the Microscopic Viewpoint

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2 CHE F213 Chemical Engineering Thermodynamics

5
Entropy
Fundamental Thermodynamic property of the system, “Entropy”

• ΔSt is a property change, independent of path (State-Function) and is given by (SBt – SAt)

• The entropy change of a heat reservoir, however, is always given by Q/T, whether the transfer
is reversible or irreversible.

• If a process is Reversible and Adiabatic, dQrev = 0; then dSt = 0

• Thus the entropy of a system is constant during a “Reversible Adiabatic Process”, and the
process is said to be “Isentropic”

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 Entropy

 Degree of “Disorderness of system”

 “Measure of molecular disorder” i.e., how atoms/molecules/ions are distributed in

a disorderly manner [Statistically defined by Boltzmann]

 Measure of “Amount of Energy Unavailable for Work” [Classically defined by

Classius]

 “Lowest for solids” and “Highest for gases”

 “Directionality & Spontaneity” of the system

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2 CHE F213 Chemical Engineering Thermodynamics

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Mathematical Statement of Second Law
Consider two heat reservoirs at TH and TC & Heat QC transferred from hot to cold reservoir,

Total entropy change:

Since TH > TC, ΔStotal is positive
Precisely, “Entropy” is the basis for the defining the direction of heat
flow from high temp to low temp for irreversible heat transfer

 The heat transferat

However, is equilibrium
reversible when
(orTHreversible
is infinitesimally
case),higher
therethan TC and
is no ΔStransfer
heat total approaches
zero possible as T = T H C

 The entropy change of any system and its surroundings, considered together, and
resulting from any real process, is positive, approaching zero when the process
approaches reversibility

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Application of Second Law to Heat-Engines

Case 1: If the engine is totally ineffective, W = 0;

(simple heat transfer between the two heat

reservoirs)

Case 2: If the process is reversible in all respects, then ΔStotal = 0,

(HE operating in a completely reversible manner is called a Carnot engine)

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Theorems

Q & W inter-convertibility  It is impossible by a cyclic process to

convert the heat absorbed by a system completely into work done by the
system.

Process directionality  No process is possible which consists solely in

the transfer of heat from one temperature level to a higher one.

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Kelvin’s Statement

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Clausius Statement

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Heat Engines: Take Away
• It is a device or machine that produce work from heat in a cyclic process.
• Cyclic process  system restored periodically to its original state
• Working fluid of a heat engine absorbs heat IQHI from hot reservoir, produces a
net amount of work W and discards heat IQCI to a cold reservoir and then return
to its initial state.
• According to first law of TD; IWI = IQHI – IQCI
• The thermal efficiency of the engine is

• Absolute-value signs are used to make the equations independent of the sign
conventions for Q and W.
• η = 100%, if QC =0, Is that possible?
• What determines the upper limit?
• Reversibility of the heat engine ?
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Reversible Cycle

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Carnot Engine & Carnot Cycle

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Carnot’s Experiment, 1824
 No engine can have a “thermal efficiency higher than
that of a Carnot engine” Step 1: A system at an initial temperature of a
cold reservoir at TC undergoes a reversible
 Thermal efficiency of a Carnot engine depends only on
the temperature levels and not upon the working adiabatic process that causes its temperature to
substance of the engine rise to that of a hot reservoir at TH. (a)
Step 2: The system maintains contact with the
hot reservoir at TH and undergoes a
reversible isothermal process during which heat
QH is absorbed from the hot reservoir.
Step 3: The system undergoes a reversible
adiabatic process in the opposite direction of
Step 1 that brings its temperature back to that of
the cold reservoir at TC.
Step 4: The system maintains contact with the
reservoir at TC, and undergoes a reversible
 a -> b Adiabatic compression isothermal process in the opposite direction of
 b -> c Isothermal expansion Step 2 that returns it to its initial state with
 c -> d Adiabatic expansion
 d -> a Isothermal compression
rejection of heat QC to the cold reservoir

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3 CHE F213 Chemical Engineering Thermodynamics

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Carnot’s Equations
For the isothermal steps; bc and da,

For an adiabatic process; ab and cd with dQ=0 becomes,

Carnot’s Equations
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Problem Statement

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Entropy Change of an Ideal Gas System

H=U+PV

(effects of P and T)

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Problem Statement

As per the first law of Thermodynamics, energy is conserved, their change in energy is zero
QH = -QC
QH + QC = 0

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CHE F213 Chemical Engineering Thermodynamics

Entropy Changes for the Ideal-Gas State

Defined Integral Functions

Defined mean Functions

integral value specific to entropy calculations

mean value specific to entropy calculations

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Problem Statement

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Entropy Balance for Open System

Rate of entropy generation,

For steady state process,

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Few Facts: Entropy Balance

There are two sources of irreversibility:

(a) those within the control volume, i.e., “internal irreversibility”

(b) those resulting from heat transfer across finite temperature differences between system and surroundings,
i.e., “external thermal irreversibility”

The limiting case, for which S

. = 0 applies when the process is completely reversible, implying:
G

The process is internally reversible within the control volume ∙ Heat transfer between the control volume and its
surroundings is reversibility.

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Lost Work: Because of Irreversibility
The “Greater the irreversibility of a process, the greater the rate of entropy
production” and
“Greater the amount of energy made unavailable for work”

Thus every irreversibility carries with it a price. Minimizing entropy production is

essential for conservation of the earth’s resources

Since,

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Problem Statement

An ideal gas at 2500 kPa is throttled adiabatically to 150 kPa at the rate of 20
mol·s–1. Determine SG and Wlost if Tσ = 300 K

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Problem Statement

Electrical to Mechanical Energy Conversion with heat dissipation

Heat & Work Equivalance Theorem: dQ = dW

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Problem Statement

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 Thanks
“All the best for your Mid Semester Exam”

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