CE2106 Week 6

Basic concept: state/path functions, process/cycle

First Law of thermodynamics: Stationary close system
 The Carnot cycle
 Entropy
Basic Concepts
State Function and Path Function
 A state function describes the equilibrium state of a system, which
depends only on the current properties of the system, not on the
path by which the system arrived at its current state. Examples
include internal energy, enthalpy, entropy.
 A path function is a function that depends on the history of the
system. Examples include work and heat.
Basic Concepts
State Function and Path Function
 The state of a simple compressible system is completely specified
by two independent, intensive properties.
 A system is called a simple compressible system in the absence of
electrical, gravitational, motion and surface tension effects.
Basic Concepts
Process Path
A process path is the series of states that a system
passes through as it moves from an initial state to a final
state.
Basic Concepts
Processes and Cycles
First Law of Thermodynamics
(also known as the conservation of energy principle)

Although energy assumes many forms, the total quantity

of energy is constant, and when energy disappears in
one form it appears simultaneously in other forms. In
simple, energy can neither be created nor destroyed; it can
only change form.

For a given system

Δ(Energy of the system) + Δ(Energy of the surroundings) = 0

First Law of Thermodynamics
Forms of Energy

Energy = capacity of a body to do work and it can be

stored and transferred

Energy = Macroscopic & microscopic forms of Energy

Macroscopic Energy = kinetic, potential, electrical,

magnetic, etc.

Microscopic Energy = atomic level / molecular structure

= Internal Energy denoted U
First Law of Thermodynamics
For a closed system

Total Energy = E

E = U + KE + PE

Total energy change between two specific states

Basic Concepts
IUPAC notation
Heat Q received from the surrounding to the system > 0;

Work received from the surrounding to the system > 0;

Adiabatic system: No Heat transfer

In notation
 Basic Concepts
Chemical Engineer notation

Heat Q received from the surrounding to the system > 0

Work received from the surrounding to the system <0

Adiabatic system: No heat transfer

Produced work by the system >0,

Notation used during this course.
First Law of Thermodynamics
For a closed system

During an interaction between a system and its surroundings, the

amount of energy gained by the system must be exactly equal to the
amount of energy lost by the surroundings.

ΔEsurr=
First Law of Thermodynamics
For a closed system
First Law of Thermodynamics
For a stationary closed system

Q-W=ΔU

Heat Q:
Heat is defined as the form of energy that is transferred
between two systems (or a system and its surroundings) by
virtue of a temperature difference
Heat:
- Conduction
- Convection
- Radiation
First Law of Thermodynamics
For a stationary closed system
Q-W=ΔU
Work:

Various forms of work:

• Mechanical work
• Moving boundary work
• Spring work
• Non-mechanical work
• Electrical work
• Magnetic work
• Electrical polarisation work
 Carnot Cycle
Nicolas Leonard Sadi Carnot:

• French ministry engineer and physicist

• Worked on early engines

• Tried to improve their efficiency

▪ Studied idealized heat engines,

cyclic processes, and
reversible processes

• Wrote his now famous paper,

“A Reflection on the Motive
Power of Fire” in 1824
▪ Introduced the “Carnot Cycle”
for an idealized, cyclic and
reversible process

http://en.wikipedia.org/wiki/Nicolas_L%C3%A9onard_Sadi_Carnot
 Carnot Cycle
Basic Concepts:
Cyclic process:
 A series of transformations by which
the state of a system undergoes
changes but the system is eventually
returned to its original state
 Changes in volume during the
process may result in external work
 The net heat absorbed by the system
during the cyclic process is equivalent Transformations of ideal gas
to the total external work done along A-B-C-D-A represents a
cyclic process
The entire process is reversible
since equilibirum is achieved
Reversible process: for each state (A, B, C, and D)

• Each transformation in the cyclic

process achieves an equilibrium state
 2-3 : Carnot Cycle
Carnot’s Idealized Heat Engine:

The Components
• A “working substance” (blue dots) is in
a cylinder (Y) with insulated walls and
a conducting base (B) fitted with an
insulated, frictionless piston (P) to which
a variable force can be applied
• A non-conducting stand (S)
upon which the cylinder may be
placed to insulate the conducting
base
• An infinite warm reservoir of heat (H)
at constant temperature T1
• An infinite cold reservoir for heat (C)
at constant temperature T2
(where T1 > T2)
 Carnot Cycle
Carnot’s Idealized Heat Engine:
The Four Processes
(1) Adiabatic Compression
The substance begins at location A
with a temperature of T2
The cylinder is placed on the stand
and the substance is compressed
by increasing the downward force
on the piston
T1 > T2
Since the cylinder is insulated, no
heat can enter or leave the substance
contained inside
Thus, the substance undergoes
adiabatic compression and its
temperature increases to T1
(location B)
 2-3 : Carnot Cycle
Carnot’s Idealized Heat Engine:

The Four Processes:

(1) Adiabatic Compression

Q = ∆U + W
QAB = 0
ΔUAB = Cv(T1 - T2)
T1 > T2

WAB = −ΔUAB
WAB = − Cv(T1 -T2 )

Adiabatic compression results in a temperature increasing.

 Carnot Cycle
Carnot’s Idealized Heat Engine:
The Four Processes:
(2) Isothermal Expansion
The cylinder is now placed on the
Q1
warm reservoir
A quantity of heat Q1 is extracted
from the warm reservoir and thus
absorbed by the substance
During this process the substance Q1 T1 > T2
expands isothermally at T1 to
State C
During this process the substance
does work by expanding against the
force applied to the piston.
 Carnot Cycle
Carnot’s Idealized Heat Engine:

The Four Processes:

(2) Isothermal Expansion
Q1
Q = ∆U + W

∆T = 0 QBC = Q1
∆UBC = 0 Q1 T1 > T2

WBC = QBC
𝑉𝑉𝐶𝐶 𝑃𝑃𝐵𝐵
𝑊𝑊𝐵𝐵𝐵𝐵 =𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑉𝑉𝐵𝐵 𝑃𝑃𝐶𝐶
 Carnot Cycle
Carnot’s Idealized Heat Engine:
The Four Processes:
(3) Adiabatic Expansion
The cylinder is returned to the stand
Since the cylinder is now insulated,
no heat can enter or leave the
substance contained inside
Thus, the cylinder undergoes
adiabatic expansion until its T1 > T2
temperature returns to T2 (State D)
Again, the cylinder does work
against the force applied to the
piston
 Carnot Cycle
Carnot’s Idealized Heat Engine:

The Four Processes:

(3) Adiabatic Expansion

Q = ∆U + W
QCD = 0
ΔUCD = Cv(T2 -T1)
T1 > T2

WCD = −ΔUCD
WCD = −Cv(T2 - T1)

Adiabatic expansion results in a temperature decreasing.

 Carnot Cycle
• Carnot’s Idealized Heat Engine:

• The Four Processes:

• (4) Isothermal Compression
Q2
•The cylinder is now placed on the
cold reservoir
•A force is applied to the piston
and the substance undergoes
isothermal compression to its
original state (State A) T1 > T2

• During this process the substance

gives up the resulting compression
heating Q2 to the cold reservoir,
allowing the process to occur
isothermally Q2
 Carnot Cycle
Carnot’s Idealized Heat Engine:

The Four Processes:

(4) Isothermal Compression
Q2
Q = ∆U +W

∆T = 0 QDA = Q2
∆UDA = 0 T1 > T2

WDA = QDA
𝑉𝑉𝐷𝐷 𝑃𝑃𝐴𝐴
𝑊𝑊𝐷𝐷𝐷𝐷 =𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 Q2
𝑉𝑉𝐴𝐴 𝑃𝑃𝐷𝐷
 Carnot Cycle
Carnot’s Idealized Heat Engine:

Net Effect:
The net work done by the substance
T1 > T2
during the cyclic process is equal to Q1
the area enclosed within ABCDA
Since the process is cyclic, the net
work done is also equal to Q1+Q2 W
The work is performed by transferring
a fraction of the total heat absorbed
from the warm reservoir to the
Q2
cold reservoir

WNET = WAB + WBC + WCD +WDA

WNET = Q1 + Q2 where: Q1 > 0 and Q2 < 0
 Carnot Cycle
Carnot’s Idealized Heat Engine:

Important Lesson:
Q1 T1 > T2

It is impossible to construct a cyclic

engine that transforms heat into work
without surrendering some heat to a W
reservoir at a lower temperature
Q2

Examples of Carnot Cycles in Practice

• Steam Engine → has a radiator
• Power Plant → has cooling towers
 Carnot Cycle

Carnot law: The efficiency of the reversible machine is the highest.

Deduction of Carnot law: The efficiency of all reversible machines is
the same.

The importance of Carnot law:

(1) In principle inequality (ηI <ηR) has solved the direction problem of
the chemical reaction;
(2) It solves the limitation problem of the thermal machine efficiency.
 Carnot Cycle

Conclusion from Carnot cycle

That is, in the Carnot cycle, the summation of heat effect

and temperature is zero.
 Statements
 Our study of the Carnot cycle showed that
Q h /Th + Q c /T c = 0.

 Since any reversible cycle can be

approximated by a series of Carnot cycles, we
expect that the integral of dQ/T along the
closed path of the cycle is 0 J.

 One consequence is that the integral of

dQ/T between a and b is independent of the
path.

 The quantity dQ/T is called the entropy dS.

 The entropy difference between a and b is

thus path independent, and entropy is a state
variable.
 Statements

 Entropy is a state variable, but Q and W are not

state variables since they depend on the path
used to get from a to b.

 For a reversible process, the change in the

entropy of the engine is opposite to the change
in entropy of the environment that provides the
heat required (or absorbs the heat generated).

 The net change in the total entropy is thus 0 J/K.

 For an irreversible process, the net change in

the total entropy will be larger than 0 J/K.
 Statements
Basic Idea and Definition:

Entropy (S) is a thermodynamic state function (describes the state

of system like p, T, and V) and is independent of path

dQrev dq rev
dS = ds =
T T
mass dependent (S) → units: J K-1
mass independent (s) → units: J kg-1 K-1

Note: Again, entropy is defined only for reversible processes…

Recall:
• Reversible processes are an idealized concept
• Reversible processes do not occur in nature
 Statements

 There are several different forms of the

second law of thermodynamics:

• It is not possible to completely change heat

into work without other change taking place.

• Heat flows naturally from a hot object to a cold

object; heat will not flow spontaneously from a
cold object to a hot object.

 Many natural processes do not violate

conservation of energy when executed in
reverse, but would violate the second law.
 Statements
 Most engines rely on a temperature
difference to operate.
 Let’s understand why:

• The steam pushes the piston to the right

and does work on the piston:
Win = nRTin(1-Vin/Vout)

• To remove the steam, the piston has to do

work on the steam:
Wout = nRTout(1-Vout/Vin)

• If Tin = Tout: Win + Wout = 0 (no net work is

done).

• In order to do work Tin > Tout and we must

thus cool the steam before compression
starts.
 Statements

 The efficiency of an engine is defined

as the ratio of the heat extracted from
the hot reservoir and the work done:

Efficiency = | W | / | QH |

 The work done and the heat extracted

are usually measured per engine
cycle.
 Because of the second law, no engine
can have a 100% efficiency!
 The cost of operation does not only
depend on the cost of maintaining the
high temperature reservoir, but may
also include the cost of maintaining
the cold temperature reservoir.
 Statements

 In many cases (heat engines), the conversion of

flow of heat to work is the primary purpose of
the engine (e.g. the car engine).
 In many other applications (heat pumps), work
is converted to a flow of heat (e.g. air
conditioning).
 The performance of a heat pump is usually
specified by providing the coefficient of
performance COP:

COP = | QL | / | W |
Question 1
 Solution (a) Heating at the constant volume and then cooling at the constant pressure.
dQ = CvdT + Pdv
Take air as ideal gas at 25oC
At the constant volume, dW=Pdv=0 , W1=0; dQ=CvdT
v, m3/kg P, kpa
For ideal gases at the constant volume, T=Pv/R , dT=Pdv/R + vdP/R= vdP/R
𝐶𝐶𝑣𝑣 𝑣𝑣 𝐶𝐶𝑣𝑣 𝑣𝑣
0.8595 100 Q=∫ 𝐶𝐶𝑣𝑣 𝑑𝑑𝑑𝑑 = ∫ 𝑑𝑑𝑑𝑑 = ∆𝑃𝑃
𝑅𝑅 𝑅𝑅
0.4298 200 5𝑅𝑅/2 × 0.8595
𝑄𝑄𝑄 = × 500 − 100 = 859.5 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
0.2865 300 𝑅𝑅
0.2149 400 For ideal gases at the constant pressure
0.1719 500 T=Pv/R , dT=Pdv/R + vdP/R= Pdv/R
0.1433 600 dQ = CvdT + Pdv
0.1228 700 𝐶𝐶𝑣𝑣 𝑃𝑃 𝐶𝐶𝑣𝑣 𝑃𝑃 𝐶𝐶𝑣𝑣 𝑃𝑃
0.1074 800 Q=∫( 𝑑𝑑𝑑𝑑 + 𝑃𝑃𝑃𝑃𝑃𝑃) = ∫( + 𝑃𝑃)𝑑𝑑𝑑𝑑 = ( + 𝑃𝑃)∆𝑣𝑣
𝑅𝑅 𝑅𝑅 𝑅𝑅
0.0955 900 5𝑅𝑅
× 500
𝑄𝑄𝑄 = 2 + 500 × 0.1719 − 0.8595 = −1203.3 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
𝑅𝑅
Cv=5R/2
CP=7R/2 W2=PΔv=500X(0.1719-0.8595)=-343.8kJ/kg
In total, Q=Q1+Q2=859.5-1203.3=-343.8 kJ/kg; W=W1+W2=-343.8 kJ/kg
ΔU=Q-W=-343.8-(-343.8)=0
 Solution (b) Isothermal compression
dQ = CvdT + Pdv
Take air as ideal gas at 25oC
For isothermal compression, dT=0 , dU=0, dQ=Pdv
v, m3/kg P, kpa
For ideal gases at the constant temperature: v=RT/P, dv=-RTdP/P2
0.8595 100 𝑅𝑅𝑅𝑅 𝑃𝑃𝑃
0.4298 200 Q=∫ 𝑃𝑃𝑃𝑃𝑃𝑃 = ∫ 𝑃𝑃 × − 𝑑𝑑𝑑𝑑 = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑃𝑃×𝑃𝑃 𝑃𝑃𝑃
0.2865 300
5
0.2149 400 𝑄𝑄 = −8.314 × 298.15 × 𝑙𝑙𝑙𝑙 = −3989.5 kJ/kmol=-138.3 kJ/kg
1
0.1719 500
0.1433 600 Q-W=0; W=Q=-138.3kJ/kg
0.1228 700
0.1074 800
0.0955 900

Cv=5R/2
CP=7R/2
 Solution (c) Adiabatic compression followd by cooling at a constant volume.
dQ = CvdT + Pdv
Take air as ideal gas at 25oC
For adiabatic compression dQ=0, and CvdT + dW=0
v, m3/kg P, kpa
For ideal gases P=RT/v
𝑅𝑅𝑅𝑅 𝑑𝑑𝑑𝑑 𝑅𝑅 𝑑𝑑𝑑𝑑
0.8595 100 𝐶𝐶𝑣𝑣 dT=- dv =-
𝑣𝑣 𝑇𝑇 𝐶𝐶𝑣𝑣 𝑣𝑣
0.4298 200
0.2865 300 𝑣𝑣
𝑇𝑇2 = 𝑇𝑇1 × ( 1 ) 𝑅𝑅/𝐶𝐶𝑣𝑣 =298.15× (
0.8595 𝑅𝑅/2.5𝑅𝑅
) =567.57 K
𝑣𝑣2 0.1719
0.2149 400
0.1719 500 dW = -CvdT
0.1433 600
5
0.1228 700 W = -Cv∆T =- 𝑅𝑅 × 567.57 − 298.15
2
0.1074 800 = −5599.9
𝑘𝑘𝑘𝑘
= −194.2 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
0.0955 900
For the cooling at the constant volume
Cv=5R/2
5
CP=7R/2 Q = CvΔT = 𝑅𝑅 × 298.15 − 567.57
2
𝑘𝑘𝑘𝑘
= −5599.9 =-194.2kJ/kg
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
Solutions
As ideal gas at 25oC

v, m3/kg P, kpa

0.8595 100
0.4298 200
0.2865 300
0.2149 400
0.1719 500
0.1433 600
0.1228 700
0.1074 800
0.0955 900
1st Law – Differential form
For a stationary closed system
Q=ΔU+W
ΔU=CVΔT

ΔH=CpΔT

dQ = cvdT + pdV
 1o law: Process Calculation for Ideal Gases
For an ideal gas in a mechanically reversible closed system
Working Equations
Isothermal process

Isobaric process

Isochoric process

Adiabatic process (with constant heat

capacities)