Chapter II: First Law of Thermodynamics

CHAPTER II

FIRST LAW OF THERMODYNAMICS

Learning Objectives
1. Solve problems involving thermodynamic properties of pure substances.
2. Apply first law of thermodynamics to open and closed system.

ZEROTH LAW OF THERMODYNAMICS

When each of two systems are in thermal equilibrium with a third system, the said two
systems are in thermal equilibrium with each other.

FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is a statement of the conservation of energy, i.e. energy
cannot be created nor destroyed, it can only be converted from one form into another. As a
consequence, this law states that the energy of the thermodynamic universe is constant.

Equations of Energy
The mathematical statement of the first law of thermodynamics is commonly called equation
of energy or energy balance. The following are the equations of energy for the different
thermodynamic systems:

A. Steady State Open System

Ws (+) Ws (-)

Q (-)
Q (+)

system Outlet (2)

u2
z2

Inlet (1)
u1
z1
Reference or datum level
Figure 2. Schematic Representation of an Open System.

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 Chapter II: First Law of Thermodynamics

For steady state system, the equation of energy for the flow system represented in Fig. 2 is

H  E K  E p  Q  Ws (17)

u 2 u 22  u12
where E K  
2 2
E p  gz  g z 2  z1 
H  H 2  H1

Q is positive (+) when energy is added to the system and negative (-) when energy is
released from the system
Ws is positive (+) when work is consumed by the system or supplied to the system (eg.
compressor, blower, fan) and negative (-) if work is produced by the system (eg.
turbine)

B. Closed System

W (+) W (-)
system
Q (+) Q (-)

Figure 3. Schematic Representation of a Closed System.

For the mass invariant system, the equation of energy is

U  Q  W (18)

where U  U 2  U1
W    pdV

Q is positive (+) when energy is added to the system and negative (-) when energy is
released from the system
W is positive (+) if work is done on the system and negative (-) when work is done by
the system

C. Isolated System

For the energy and mass invariant system, the energy equation is

U  0 (19)

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 Chapter II: First Law of Thermodynamics

Thermodynamics of Ideal Gas in Closed System

The ideal gas is the simplest physical model of a gas. In chemical engineering, it is always
convenient to use the ideal gas model as a benchmark to compare the processes of a real
system. Table 5 summarizes the equations that govern thermodynamic processes of ideal
gases in closed system.

These equations are derived using equation 13, the equation of energy for closed system, and
the following:

H  U  PV  (20)

H   C p dT (21)

U   CV dT (22)

Q  TdS (23)

W  PdV (24)

C p  CV  R (25)

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 Chapter II: First Law of Thermodynamics

THERMODYNAMIC DEFINITIONS
Table 1. Thermodynamic Definitions.

Enthalpy H  U  PV

Gibbs Free Energy G  H  TS

Helmholtz Free Energy A  U  TS

 U 
Constant-volume heat capacity CV   
 T V

 H 
Constant-pressure heat capacity CP   
 T  P

Coefficient of thermal expansion, 1  V 

  
Volume expansivity V  T  P

1  V 
Isothermal compressibility T    
V  P  T

  V  
V  T   
Joule-Thomson coefficient   T  P 
 
CP

A thermodynamic process is a change of a system from one state to another.

Common thermodynamic processes

1. isothermal – constant temperature process

2. isobaric- constant pressure process

3. isometric or isochoric – constant volume process

4. adiabatic process – a process where there is no heat evolved from or heat added to the
system

5. isentropic – constant entropy process

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Table 3. Summary of Thermodynamic Processes of Ideal Gases in Closed System.

PVT
Process
Characteristic Relationship H U Q W

V2 V2
Isothermal R ln  R ln
T=constant PV=constant 0 0 V1 V1

T2
 C p dT or T2
  PV
T1
Isobaric P=constant V/T=constant CV dT H
U  PV T1

T2
Isochoric 
T1
C p dT
or T2

Isometric
V=constant P/T=constant or  CV dT U 0
U  VP
T1

 1
 
RT1   P2   
TV  1  cons tan t T2 T2  1   
Adiabatic Q=0 
T1
C p dT T1
CV dT 0   1   P1  
 

 n 1
  n 1

n   RT1  P2  n RT1  P2  n
 1    1
n  1  1  P1 
T2

T2
Polytropic PVn=constant PVn=constant
T1
C p dT  T1
CV dT



n  1  P1 




Cpms/R = A + B TLM + TAM TLM [ C + D/(T1T2)2 ] where: TLM = (T2 – T1)/ln(T2/T1), TAM = (T1 + T2)/2

Cpmh/R = A + B TAM + (C/3) [ 4TAM2 – T1T2 ] + D/(T1 T2)

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 Chapter III: Heat Effects

CHAPTER III

HEAT EFFECTS

Learning Objectives
1. Solve problems involving thermodynamics related to phase change, heat transfer effects
and reaction.
2. Recognize the use of thermodynamic diagrams in solving problems.

Heat

Closely related to temperature changes is the transient form of energy called heat. We
can observe that whenever a difference in temperature exists, heat transfers from a body at a
higher temperature to a body at lower temperature. This manifestation of energy transfer is
known as heat transfer. In mathematical equation, heat given off by a body (an exothermic
process) is denoted by a negative quantity while heat taken on by a body (an endothermic
process) is positive. The unit of heat is joule and the symbol is Q.

Q = UA ∆T (26)

Where : Q – rate of heat transfer

U – empirical coefficient, over-all heat transfer coefficient
A – area for heat transfer
∆T – change in temperature

Q = ∫Cp ∆T if ∆KE, ∆PE, Ws = 0 (27)

The Heat Balance Equation

∑ Heat inputs - ∑ Heat outputs = Accumulation (28)

At steady state, accumulation = zero and

∑ Heat inputs = ∑ Heat outputs (29)

Energy Balances for Reactive Systems

A. Heats of Reaction

The heat of reaction, Hˆ R T , P  is the difference between the enthalpy of products and the
enthalpy of the reactants for a reaction taking place under the following conditions:

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1. Reactants are fed in stoichiometric amount and the reaction goes to completion
2. Reactants and products are at the same temperature and pressure

The standard heat of reaction, Hˆ 0 R T , P  is the heat of reaction when both the reactants and
products are at a reference temperature and pressure usually at 25 0C and 1 atm.

If the heat of reaction is positive, the reaction is considered to be endothermic and if otherwise,
the reaction is exothermic. The properties of heat of reaction depend on the phases of reactants
and products.

Hess’s Law

If the stoichiometric equation for a reaction can be derived from other reaction equations (by
multiplication by constants, addition and subtraction) then the heat of reaction for the first
reaction can be derived by performing the same algebraic operations on the heats of reaction for
the other reactions.

Using Hess’s Law the standard heat of reaction can be derived from the standard heat of reaction
can be derived from the standard heat of formation. The heat of formation, Hˆ f T , P  for a
0

chemical species is defined as the heat of reaction at standard conditions for the reaction forming
1 mole of this species from the elements which make it up. Thus,

Hˆ R0   v Hˆ    v Hˆ 

products
i
0
f i
reac tan ts
i
0
f i
(30)

where vi – is the stoichiometric coefficient of the ith species.

B. Heat of Combustion

The standard heat of combustion Hˆ C T , P  is the heat of the reaction of a substance with
0

oxygen to form specified products with both reactants and products at standard conditions,
usually at 25 0C and 1 atm.

Energy Balance

In solving energy balance problems for reactive processes, the procedure is the same with that of
non-reactive systems except in the calculations of enthalpy change associated with chemical
reactions.

A hypothetical path may be constructed since enthalpy is a state function. Consider a reaction
taking place in a reactor,
aA + bB cC + dD (31)

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c moles of C
a moles of A
b moles of B
Reactor d moles of D
T2
T1

Suppose the process is steady state and the reaction proceeds to completion. Using energy
balance, the amount of heat transferred during the process may be calculated.

For a steady state process, Equation (32) is applicable

(H  KE  PE ) flowing stream s  Q  Ws (32)

Neglecting changes in PE and KE and since there is no shaft work, Ws = 0. Thus the above
equation reduces to

Q = ΔH (33)

To calculate the change in enthalpy, a hypothetical process path may be created. The process
path may include the following steps:

Step a: Cooling down the reactant’s temperature at constant pressure from T1 to 25 0C.
Step b: Reaction of A and B to yield C and D
Step c: Heating of the products from 25 0C to T2 at constant pressure

The hypothetical path may be illustrated as follows:

Q = H
A, B C, D
T1, 1 atm T2, 1 atm

Step a Step c

A, B C, D
25 0C., 1 atm Step b 25 0C., 1 atm

The total change in enthalpy is the sum of all the enthalpy changes in each step:

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 Chapter III: Heat Effects

H  H a  H b  H c (34)
where
H a   
250 C
cpi dT (35)
T1
i

H b  Hˆ R0  H
products
0
f  H
reac tan ts
0
f
(36)

H c   
T2
cpi dT (37)
250 C
i

Heat Quantities in Heat Balance without Reaction:

Sensible Heat and Latent Heat

Sensible heat is the change in the internal energy or enthalpy of a substance if it is

heated or cooled from T 1 to T 2 without undergoing a change in state. This definition
applies to gases, liquids, and solids.

For a solid, sensible heat , ∆H = ∫T 2 n Cp, solid dt (38)

For a liquid, sensible heat , ∆H = ∫T 2 n Cp , liquid dt (39)

For a gas, sensible heat , ∆H = ∫T 2 n Cp , gas dt (40)

Where
T1 is the initial temperature
T2 is the final temperature
n is the mol of substance
Cp, solid is the heat capacity of solid
Cp, liquid is the heat capacity of liquid
Cp, gas is the heat capacity of gas

For processes that take place at constant volume, we have to replace Cp by Cv.

Latent Heat is the heat required to change a quantity (mass or mol) of a substance from
one state to another. This occurs at constant temperature and the energy involved is
responsible for the rearrangement of the molecules in changing the state.

Latent Heat of Fusion is the heat required to melt a solid to form its liquid state. The
reverse is latent heat of solidification, which is the heat evolved when a liquid freezes.
The two latent heats for a particular substance are equal in magnitude but opposite in
sign.

Latent Heat of Vaporization is the heat needed to vaporize liquid.

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Latent heat of condensation is the opposite. This is the heat given off when a vapor
condenses.

Latent heat of sublimation is the heat involved when a solid changes directly to gas.
This is the heat needed in the sublimation of dry ice (solid CO 2 ) at 1 atm.

Heat Capacity of Solids and Liquids

Cp Obtain from experiments

Cp = a + bT (41)
Cp = a + bT – c/T 2 (42)

Where
a, b, and c are constant

Heat Capacity of Gases

From calculations employing statistical mechanics and kinetic theory of gases, heat
capacity of monoatomic gases such as krypton, argon, etc. is

Cv = 5/2 R; Cp = 7/2 R Cp - Cv = R (43)

Where
R = ideal gas constant = 8.314 kJ/ (kmol K)

For other gases, the heat capacity is a function of temperature. This temperature
dependence can be experimentally determined and expressed as empirical relations.

Cp = a + bT + cT 2 + dT 3 + eT 4 +...+ (44)

Where
a, b, c, and d are constant that depend on the type of molecules
T = is the temperature in K

Using the relation Cp – Cv = R, we can express Cv as

Cv = a + bT + cT 2 + dT 3 + eT 4 – R (45)

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Example 1:

What is the heat capacity of carbon dioxide at 100 oC?

Example 2:

Find the change in enthalpy involved in heating 100 kg of carbon dioxide from 23 0 C to
7000 C.

Heat Capacity of Mixtures of Gases

The heat capacity of a mixture of gases depends on the mole fraction of each
component. The following formula is valid when no interaction betwe en different kinds
of molecule exist so that no heat is involved in mixing.

Cpmix = y1 Cp1 + y2 Cp 2 + y3 Cp 3 +........yn Cp n = ∑y1 Cp1

Where: y1 : mole fraction of component ί

Cp : heat capacity of component ί

Example 3:

Find the heat capacity of a gas mixture consisting of 12% CO 2 , 3% CO, 6% O 2 ,

74% N 2 , and 5% H 2 O at 200 0 C. What is the change in enthalpy in cooling 10kmol of this
mixture from 1000 0 C to 200 0 C at constant pressure?

Example 4:

A gas stream containing 60 weight % ethane and 40% n-butane is to be heated

from 150K to 250K at a pressure of 5 bars. Calculate the required heat input per kg of the
mixture, neglecting potential and kinetic energy changes. Assume ideal gas behavior.
H ethane (250K, 5 bar): 973.3 kJ/kg
H ethane (150K, 5 bar): 314.3 kJ/kg
H n-butane (250K, 5 bar): 237 kJ/kg
H n-butane (150K, 5 bar): 30 kJ/kg

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 Chapter IV:

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 Chapter V: Second Law of Thermodynamics

CHAPTER V

SECOND LAW OF THERMODYNAMICS

Objectives
1. Solve problems involving thermodynamic properties of pure substances.
2. Apply the first and second law of thermodynamics to open and closed system.

Introduction
Second Law provide means for
1. predicting the direction of processes
2. establishing conditions for equilibrium
3. determining the best theoretical performance of cycles, engines and other devices
4. evaluating quantitatively the factors that preclude the attainment of the best theoretical
performance level
Additional uses includes its roles in
5. defining a temperature scale independent of the properties of any thermometric substance
6. developing means for evaluating properties such as U and H in terms of properties that
are more readily obtained experimentally

Statements of the Second Law of Thermodynamics

A. The Principle of Thomson (Lord Kelvin)

It is impossible by a cyclic process to take heat from a reservoir and to convert it into
work without simultaneously transferring heat from a hot to a cold reservoir.

B. The Principle of Clausius

It is impossible to devise an engine which, working in a cycle, shall produce no effect

other than the transfer of heat from a colder to a hotter body.
T2
higher
Q2
impossible

Q1
lower
T1

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 Chapter V: Second Law of Thermodynamics

C. The Principle of Planck

It is impossible to devise an engine, which working in a complete cycle will produce no

effect other than raising of a weight and the cooling of a heat reservoir.

T W cycle ≤ 0
Impossible
Q cycle ≤ 0
Q

W
T
Q

D. Mathematical Statement of the Second Law of Thermodynamics

S Total  0 (26)

S system  S surroundings   0 (27)

Irreversible: if the system and all parts of its surroundings cannot be exactly restored to their
respective initial sates after the process has occurred.
Examples:
1. heat transfer through a finite temperature difference
2. unrestrained expansion of a gas or liquid to a lower pressure
3. spontaneous chemical reaction
4. spontaneous mixing of matter at different compositions or states
5. Friction – sliding friction as well as friction in the flow of fluids
6. electric current flow through a resistance
7. magnetization or polarization with hysteresis
8. inelastic deformation

Internal irreversibilities: those that occur within the system

External irreversibilities: those that occur within the surroundings

Reversible: if the system and all parts of its surroundings can be exactly restored to their
respective initial state after the process has taken place.
: can come back to its original state by taking the same path.
Examples:
1. Pendulum oscillating in an evacuated space
2. System consisting of a gas adiabatically compressed and expanded in a frictionless
piston-cylinder assembly.
3. Two bodies at different temperature that is able to communicate thermally.

Internally reversible process: one in which there are no internal irreversibilities.

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 Chapter V: Second Law of Thermodynamics

Cycle Energy Balance

Energy balance for any system undergoing a thermodynamic cycle:

∆ E cycle = Q cycle - W cycle (30)

Since no net change in its energy, since the system is returned to its initial state after the
cycle:

W cycle = Q cycle

Perpetual Motion Machine

Create work from nothing or create mass or energy (Violates 1st law)
Extract heat from a source and then convert this heat completely into other forms of energy.
(Violates 2nd law)
A perpetual machine would have no friction and thus would run indefinitely but produce no
work.

Perpetual Motion Machines

First Kind: Refer to processes that led to a net change in the energy of the universe.
Second Kind:

High Temperature

QH QH
W = QH
Heat
Wout = W-W’ W’ = QH - QL Pum
= QL p
QL

Low Temperature

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 Chapter V: Second Law of Thermodynamics

Heat engines or Thermal engine

 A machine that produces work from heat in a cyclic process

 Closed system that exchanges only heat and work with its surrounding an that operates in
cycles

Elements of heat engine

1. Working substance: matter, fluid that receives heat, rejects heat and does work.
2. Source of Heat (hot body, heat reservoir, source): from which the working substance
receives heat

3. Heat Sink (receiver, a cold body, sink): to which the working substance can reject heat
4. Engine: wherein the working substance must do work or have work done on it.

Two classes:

Hot Body Hot Body

Q in Q out

W cycle = Q in – Q out
System
W cycle = Q out – Q in
out
Q in
Q out
Cold Body Cold Body

Power Cycles Refrigeration and

Heat Pump Cycles

Power Cycles: deliver a network transfer of energy to their surroundings during each cycle.
W cycle = Q in - Q out (31)

Thermal Efficiency,
W cycle Q in – Q out
Q out
N = = = 1 -
Q in Q in Q in
(32)
* N cannot be greater than unity, always less than unity. In actual efficiency, it is lower
than the power cycle thermal efficiency.

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 Chapter V: Second Law of Thermodynamics

Heat Engines: a machine that produces work from heat in a cyclic process.

BOILER
T
U
R
B Ws
I
Ws N
E
CONDENSER

Steam Power Plant

1. Liquid water approximately ambient temperature is pumped into a boiler a high pressure.
2. Heat from a fuel (heat of combustion of a fossil fuel or heat from a nuclear reaction) is
transferred in the boiler to the H2O, converting it o high temperature steam at the boiler
pressure.
3. Energy is transferred as shaft work from the steam to the surrounding by a device such as
turbine, in which the steam expands or reduced pressure and temperature.
4. Exhaust steam from the turbine is condensed at low temperature and pressure by the
transfer of heat to cooling H2O.

W = /QH/ - /QC/

Network output W /QH/ - /QC/ /Qc/

N= = = = 1-
Heat input /QH/ /QH/ /QH/

Carnot Cycle

 Sadi Carnot (1796 – 1832)

 Ideal heat engine that operates cyclically and reversibly between two temperatures
1. System initially in thermal equilibrium with a cold reservoir at temperature. TC
undergoes a reversible adiabatic process that causes its temperature to rise to that
of a hot reservoir at TH.
2. 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.
3. The system undergoes a reversible adiabatic process in the opposite direction of
step 1 that brings is temperature back to that of the cold reservoir at TC.

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 Chapter V: Second Law of Thermodynamics

4. The system maintains contact with the reservoir a TC and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns it to its initial
state with rejection of heat /QC/ to the cold reservoir.

Carnot Principles
1. The thermal efficiency of an internally irreversible heat engine is always less than the
thermal efficiency of an internally reversible heat engine operating with heat transfer at
the same high- and low-temperature regions.
2. The thermal efficiencies of two internally reversible heat engines operating with heat
transfer at the same high- and low-temperature regions are equal.

The Carnot heat engine consists of four steps: reversible isothermal expansion (A→B),
reversible adiabatic expansion (B→C), reversible isothermal compression (C→D), and
reversible adiabatic compression (D→A).

P B

D
C

V
Fig 4. Carnot Cycle

A Carnot heat engine is an ideal cycle since all the steps are reversible processes.

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 Chapter V: Second Law of Thermodynamics

Carnot’s engine efficiency

 Efficiency of a Carnot engine approach unity only when TH approaches infinity or TC
approaches zero.
 All heat engines operate at η less than unity.
 Two reversible device working at the same temperature limits will have the same η

Carnot’s engine efficiency

ηactual = ηcarnot (reversible process)
ηactual < ηcarnot (irreversible process)
ηactual > ηcarnot (violates 2nd law)

Thermodynamic Temperature and the Ideal Gas Scale

Carnot engine based on ideal gas is reversible in nature.

PV Diagram Evaluation
4 – 1, D-A: A reversible adiabatic compression until temperature reaches, TH
1 – 2, A-B: An isothermal expansion with absorption of heat, QH.
2 – 3, B-C: A reversible adiabatic expansion until temperature reaches, TC or TL.
3 – 4, C-D: An isothermal compression with rejection of heat.

Reversible Adiabatic Compression (4 – 1, D-A)

∆U = Q + W
PdV = -nCv dT
-Cv dT = dV
R T V
(Cv/R) ln (Tc/TH) = ln (V1/V4) (33)

Isothermal Expansion (1-2, A-B), QH

dQH = Cv dT + PdV
dQH = PdV
but, PV = RT
QH = RTH ln (V2/V1) (34)

Reversible Adiabatic Expansion (2 – 3, B-C)

-dQ = Cv dT + PdV
-CvdT = PdV
-Cv/R dT/T = dV/V
(Cv/R) ln (Tc/TH) = ln (V2/V3) (35)

Isothermal Compression (3 -4, C-D), Qc

Equation derived from the above correlations

Qc = RTc ln (V4/V3) (36)

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Combining equations (34) and (36)

QH = TH ln (V2/V1)
QC TC ln (V3/V4) (37)

Combining equations (1) and (3)

ln (V1/V4) = ln (V2/V3) same as
ln (V3/V4) = ln (V2/V1) (38)

Equation derived from the above correlations

Combining equations (38) to (37):

(QH / QC) = (TH/TC) (39)

Recalling engine efficiency equation:

η = W/QH = (QH – QC) / QH
= 1 – (QC/QH) (40)
= 1 – (TC/TH) (41)

Reversed Carnot engine

When mechanical work is supplied as an energy input and heat may be moved from one energy
value (temperature) to another energy value.
Carnot heat pump: operates in a reverse heat engine.
Transfer of heat from cold to warm is also possible, if work is done on engine.

COP: The heat supplied to the cycle at a low temperature (the desired effect) divided by the net
work. Measure of performance of a refrigeration.

Coefficient of Performance (COP)

COP = QC / W (42)
since: W = QH – QC or
W + QC = QH
then: COP = QC/(QH-QC)
= (QC/QH) – 1 (43)
= (TC/TH) – 1 (44)
= TC/(TH-TC) (45)
also: QC/(QH-QC) = TC/(TH-TC) (46)

Based on reversed Carnot engine (refrigeration)

COPC = TC/(TH-TC) (47)

Based on Carnot engine (heat generation)

COPH = TH/(TH-TC) (48)

Lecture Notes for ChE 307: ChE Thermodynamics I 36

by: Mary Rose B. Flores-Persincula
 Chapter V: Second Law of Thermodynamics

Same PV diagram applies for the reversed Carnot engine.

Entropy
A. Change in Entropy of a Heat Reservoir

Heat reservoir is a body of infinite heat capacity. The change in entropy of a heat reservoir is
computed using

Q
S  (49)
T

P B
C

B. Entropy Balance for a Control Volume

Time rate entropy change = net rate of energy transfer due to mass flow -
net rate of entropy transfer due to heat transfer +
rate of entropy production due to irreversibilities


dS cv   n Q 
  mi Si   mo So     cv
j
(50)
dt in out j 1 T j

Lecture Notes for ChE 307: ChE Thermodynamics I 37

by: Mary Rose B. Flores-Persincula
 Chapter V: Second Law of Thermodynamics

C. Change in Entropy of an Ideal Gas

Table 4. Summary of Change in Entropy of Ideal Gas

Process Governing equation
Any process T 2 C dT V
S   V
 R ln 2
T1 T V1
T 2 C dT P
S   P
 R ln 2
T1 T P1
Isothermal expansion into a vacuum V  P 
S  nR ln  2   nR ln  1 
 V1   P2 
Isobaric T2 dT
S   C p
T1 T
Isochoric T2 dT
S   CV
T1 T

Isentropic
Process is reversible and adiabatic
dQrev = 0, therefore, dSt = 0.

Entropy is constant during a reversible adiabatic process.

Irreversible
When a system undergoes an irreversible process from one equilibrium state to another, the
entropy change of the system must be evaluated by application of the equation to an arbitrarily
chosen reversible process that accomplishes the same change of state as the actual process.
Integration is not carried out for the irreversible path.

Entropy of Cycle
∆Scycle = 0, reversible
∆Scycle > 0, irreversible
∆Scycle < 0, impossible

Irreversible, treat them as reversible and perform ∆St = ∫(dQrev /T), then apply relationship of
reversible to irreversible.

Ideal Work
The ideal work is the shaft work of a completely reversible process. For a single stream flowing
through the control volume
Wideal  H  T S (51)

Lecture Notes for ChE 307: ChE Thermodynamics I 38

by: Mary Rose B. Flores-Persincula
 Chapter V: Second Law of Thermodynamics

Lost Work
Lost work is the work wasted due to irreversibility. It is defined as the difference between the
actual shaft work and ideal work.

Wlost  T S G (52)

THIRD LAW OF THERMODYNAMICS

The third law of thermodynamics is based on experimental evidence. It states that the entropy
change for isothermal processes at absolute zero temperature is zero. By convention, the entropy
of a pure crystalline substance is taken to be zero at absolute zero temperature.

S = ∫0Tf (Cp)s (dT/T) + (∆Hf/Tf) + ∫TfTv (Cp)l (dT/T) + (∆Hv/Tv) + ∫TvT (Cp)g (dT/T) (53)

Lecture Notes for ChE 307: ChE Thermodynamics I 39

by: Mary Rose B. Flores-Persincula