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Changing the Internal Energy

The internal energy of a system would decrease if the system gives
off heat or does work. Therefore, internal energy of a system
Thermodynamics increases when the heat increases (this would be done by adding
heat into a system). The internal energy would also increase if work
were done onto a system. Any work or heat that goes into or out of
a system changes the internal energy.
ΔU, the total change in internal energy of a system, is a state
function that is independent of the path taken to change the
Department of Biomedical Engineering system's state.
Faculty of Applied Science

ⅈ
∆𝑈 = n𝑅∆𝑇 (J)
2
1 2

The First Law of Thermodynamics The First Law of Thermodynamics

• The first law of thermodynamics states that when a system

undergoes a change from one state to another, the change
in its internal energy is
U = Q + W
• where Q is the energy transferred into the system by heat
and W is the work done on the system.
• Although Q and W both depend on the path taken from the
initial state to the final state, the quantity U does not depend
on the path.

Won done on the system

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The First Law of Thermodynamics Work done on the system

• Q: heat transferred to the system. Work done on the system
• Q’=-Q: heat transferred from the system
→ →
• Q>0 : the system really receives energy
dW = F.ds = P.S.dy = −PdV
• Q<0, Q’>0: the system releases energy as heat

V2
• W: work done on the system.
• W’=-W: work done by the system. Won = −  PdV
• W>0: work is really done on the system V1
• W<0,W’>0: work is really done by the system.
Won done on the system (air compression W >0)
Wby done by the system (air expansion W<0)
Won = - Wby
5 6

Work done on the system The First Law of Thermodynamics

Work is a path function. Path functions depend on the path taken to
reach one state from another.

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Application of The 1st Law of TD Application of The 1st Law of TD

Isothermal process of an Ideal Gas Isobaric process P=const
V
T = const = PV = const P = const : = const
T
U = Q + W
1st Law of TD U = Q + W

U =
i
nRT = 0;Q = −W
Work done on the system W = − PdV = −PV = −nRT
2
(2) V2
nRT dV = −nRT ln V2
Heat transferred to the system Q = U − W
W = −  PdV = −  i i+2
(1) V1
V V1 Q = nRT + nRT = n R T
2 2
V2
Q = −W = nRT ln C pm
V1 Q = nCp.mT
i+2
The molar specific heat C p.m = R
9 at constant pressure 2 10

Application of The 1st Law of TD Specific heat in thermodynamic process

Isochoric Process V=const

1st Law of TD

Work done on the system

Heat transferred to
the system

The molar specific heat

at constant volume

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Application of The 1st Law of TD Application of The 1st Law of TD

Adiabatic process Q=0 Adiabatic process Q=0

Heat transferred to
the system

Work done on the system

14
The ratio of the molar
specific heat for the gas

The molar specific heat

at constant pressure

The molar specific heat

at constant volume
13

Quiz
Identify the nature of path A, B, C and D

D: Isobaric

A: Isochoric C: Isothermal

B: Adiabatic Q=0
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Quiz Quiz
The figure here shows five paths traversed by a gas on a p-V diagram.
Rank the paths according to the change in internal energy of the gas, What amount of heat is to be transferred to nitrogen (N2) in
greatest first. an isobaric heating process so that the gas may perform 2 J
ⅈ work?
∆𝑈 = n𝑅∆𝑇
2
5>1=2=3=4

17 18

Quiz Quiz
Two moles of an ideal gas at 300K were cooled at constant volume so that the pressure
is reduced to half the initial value. Then as a result of heating at constant pressure, the Heat transfer from a to c in
gas expands till it attains the original temperature. Find the total heat absorbed by the isothermal process
gas.

the total heat absorbed by the gas is Prove That Heat Transfer Is Path Function

System received heat 19 20

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Quiz Quiz
Three moles of an ideal gas being initially at a temperature Ti​=273 K were isothermally One mole of oxygen being initially at a temperature T0​=290 K is
expanded 5 times its initial volume and then isochorically heated so that the pressure adiabatically compressed to increase its pressure to 10.0 times. Find:
in the final state become equal to that in the initial state. The total heat supplied in the (a) the gas temperature after the compression;
process is 80 kJ. Find the ratio of the molar specific heat for the gas  = CP/CV . (b) the work that has been performed on the gas.
Adiabatic process
Heat transfer during The total heat supplied in the process (a) the gas temperature after
isothermal process the compression
The molar specific heat at constant volume

Heat transfer during

isochoric process The ratio of the molar specific heat

(b) the work that has been performed on the gas

21 22

REVERSIBLE – IRREVERSIBLE PROCESS QUASI-STATIC vs QUICK PROCESS

In a reversible process, the system can be returned to its initial
conditions along the same path on a PV diagram, and every point
along this path is an equilibrium state.
A process that does not satisfy these requirements is irreversible.

P P
1 Quasi–static 1 irreversible Quick (sudden) -
process process
P P
2 1 Quasi–static Quick (sudden) -
2 1
process process
reversible irreversible
2 2

V V reversible irreversible

23 V V 24

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Irreversible process Kelvin–Planck form of the second law of thermodynamics

Example It is impossible to construct a heat engine that, operating in

– The transfer of heat goes from a cycle, produces no effect other than the input of energy by
heat from a reservoir and the performance of an equal
the hot object to the cold amount of work (the Kelvin–Planck statement).
object..
– In diffusion, particles move Meaning: It is impossible to construct an engine whose sole purpose
is to convert the heat from a high-temperature source/reservoir into
from an area of higher an equal amount of work.
Heat is transferred to the surrounding environment during all energy
concentration to one of lower conversions
Consequently, not all energy transferred by heat can be converted
concentration until equilibrium into work, and some of it is lost in the form of waste heat.
is reached. 25 26

Heat engine Heat engine

A heat engine carries some working
substance through a cyclic process On the PV diagram, a cyclic
process of heat engine is/has :
during which
- closed curve.
(1) the working substance absorbs - clockwise direction (W<0)
energy by heat from a high- - the area enclosed by the curve
temperature energy reservoir
= /W/
(2) work is done by the engine
PV diagram for an arbitrary
(3) energy is expelled by heat to a cyclic process taking place in an
engine. The value of the net
lower-temperature reservoir work done by the engine in one
cycle equals the area enclosed
by the curve.
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Heat engine The Efficiency of a Heat Engine

The thermal efficiency e of a heat engine is defined as the ratio of the
net work done by the engine during one cycle to the energy input at the The Efficiency of an Engine Work_ done _ by _ the _ engine W'
e= =
higher temperature during the cycle Heat _ received_ from_ hot _ reservoir Q h

Engine operates in a cycle process, the change in internal energy is 0:

U = Qh + Qc + W = 0
through a cycle, its initial and final Work done by the engine: W ' = − W = Q h + Qc = Q h − Q'c
internal energies are equal, and so
W ' Q h − Q'c Q'
e= = = 1− c
Qh Qh Qh

29 30

Heat engine Heat engine

A heat engine has 100% efficiency (e = 1)
• An engine transfers 2.00 x 103 J of energy from only if /Qc/ = 0, if no energy is expelled to
a hot reservoir during a cycle and transfers the cold reservoir. In other words, a heat
engine with perfect efficiency would have to
1.50 x 103 J as exhaust to a cold reservoir. expel all of the input energy by work.
(A)Find the efficiency of the engine.
(B)How much work does this engine do in one
cycle?

Q'c 1.5  103 It is impossible to construct such a perfect

e = 1− = 1− = 25% engine. On the basis of the fact that
Qh 2  103 efficiencies of real engines are well below Schematic diagram of a heat
100% (e <1)
W ' = Q h − Q'c = (2  103 ) − (1.5  103 ) = 0.5  103 J engine that takes in energy from a
hot reservoir and does an
equivalent amount of work
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The Carnot Engine The Carnot Engine

• The engine operates in a cyclic process consisting of 2
isothermal processes and 2 adiabatic processes.
V
VB Tc ln( C )
AB : isothermal : Q AB = nRTh ln( )0 System Q'c VD
VA received e = 1− = 1−
Qh V
BC : adiabatic : Q BC = 0 heat Th ln( B )
VA
VD System
CD : isothermal : QCD = nRTc ln( )0
VC released BC : adiabatic : TV  −1 = const Th VB −1 = Tc VC −1
Heat
DA : adiabatic : Q DA = 0 DA : adiabatic : TV  −1
= const Th VA −1 = Tc VD −1
V
Q h = Q AB = nRTh ln( B ) VB VC
VA =
VA VD
V
Q'c = −QCD = nRTc ln( C )
VD
Tc Increase Th to increase efficiency→
e = 1−
V
Tc ln( C ) operate in pressure vessel to increase
Q'c VD
e = 1− = 1− Th pressure → increase temperature
Qh V
Th ln( B )
VA 33 34

The Carnot Engine The Carnot Engine

• A heat engine operating in an ideal, Hydrogen is used in a Carnot cycle as a working substance. Find the
reversible cycle using an ideal gas—called
Adiabatic
efficiency of the cycle, if as a result of an adiabatic expansion
a Carnot cycle—between two energy processes (a) the gas volume increases n=2.0 times;
reservoirs is the most efficient engine
possible.
• The Carnot cycle consists of two adiabatic Adiabatic expansion
processes and two isothermal processes, adiabatic
all reversible. expansion
• No real heat engine operating between
two energy reservoirs can be more
efficient than a Carnot engine operating
between the same two reservoirs.
Tc
e max = eCarnot = 1 −
Th 𝑖+2
Diatomic gas with i=5  =
• All real engines are less efficient than the 𝑖
Carnot engine because they do not
operate through a reversible cycle. efficiency
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The Carnot Engine Clausius form of the second law of thermodynamics

Hydrogen is used in a Carnot cycle as a working substance. Find the It is impossible to construct a cyclical machine whose sole effect is to
efficiency of the cycle, if as a result of an adiabatic expansion
transfer energy continuously by heat from one object to another
(b) the pressure decreases n=2.0 times.
object at a higher temperature without the input of energy by work
Adiabatic expansion
(the Clausius statement).
adiabatic
expansion • Energy does not transfer spontaneously by
heat from a cold object to a hot object.
• A refrigerator is a device that uses work in
order to transfer energy from a low
temperature reservoir to a high-temperature
Efficiency of the cycle reservoir as the device continuously repeats a

37 set series of thermodynamic processes. 38

Refrigerator (Heat bump) Refrigerator (Heat bump)

Refrigerator (Heat bump) is an
On the PV diagram, a cyclic process
engine that
of Refrigerator (Heat bump)
• having an input of energy by work
is/has :
• taking in energy /Qc/ from a cold
- closed curve.
reservoir
- counterclockwise direction (W>0)
• expelling energy /Qh/ to a hot
- the area enclosed by the curve =
reservoir
/W/
• operating through a cyclic process

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Refrigerator (Heat bump) Refrigerator

Coefficient of Performance (COP) (cooling mode) The effectiveness of a heat pump /refrigerators is described
in terms of a number called the coefficient of performance
heat _ received _ from _ cold _ reservoir Qc
COP COP COP(cooling mod e) = =
Work _ done _ on _ the _ refrigerator W
U = Q h + Qc + W = 0
through a cycle, its initial and final W = − Q h − Q c = Q 'h − Q c
internal energies are equal, and so
𝑄𝑐
𝐶𝑂𝑃(𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑚𝑜𝑑𝑒) =
𝑄′ℎ − 𝑄𝑐
𝑇𝑐
𝐶𝑎𝑟𝑛𝑜𝑡_𝑐𝑦𝑐𝑙𝑒: 𝐶𝑂𝑃(𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑚𝑜𝑑𝑒) =
𝑇ℎ − 𝑇𝑐
(the maximum COP for a heat pump in its cooling mode)
41 43

Heat bump Refrigerator (Heat bump)

ℎ𝑒𝑎𝑡_𝑑𝑒𝑙𝑖𝑣𝑒𝑟𝑒𝑑_𝑡𝑜_ℎ𝑜𝑡_𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 𝑄′ℎ
𝐶𝑂𝑃(ℎ𝑒𝑎𝑡𝑖𝑛𝑔 mod 𝑒) = = An impossible heat pump or
𝑊𝑜𝑟𝑘_𝑑𝑜𝑛𝑒_𝑜𝑛_𝑡ℎ𝑒_ℎ𝑒𝑎𝑡𝑝𝑢𝑚𝑝 𝑊
refrigerator—that is, one that takes in
Δ𝑈 = 𝑄ℎ + 𝑄𝑐 + 𝑊 = 0 energy from a cold reservoir and expels
𝑊 = −𝑄ℎ − 𝑄𝑐 = 𝑄′ℎ − 𝑄𝑐
𝑄′ℎ an equivalent amount of energy to a
𝐶𝑂𝑃(ℎ𝑒𝑎𝑡𝑖𝑛𝑔 mod 𝑒) = hot reservoir without the input of
𝑄′ℎ − 𝑄𝑐
𝑇ℎ energy by work.
𝐶𝑎𝑟𝑛𝑜𝑡_𝑐𝑦𝑐𝑙𝑒: 𝐶𝑂𝑃(ℎ𝑒𝑎𝑡𝑖𝑛𝑔 mod 𝑒) =
𝑇ℎ − 𝑇𝑐
(the maximum COP for a heat pump in its heating mode)

Impossible heat pump

44 45

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Summary Quiz
A refrigerator has a coefficient of performance (COP) equal to 5.00. The
refrigerator takes in 120 J of energy from a cold reservoir in each cycle. Find
𝑊′ 𝑄ℎ − 𝑄𝑐′ 𝑄𝑐′ (a) the work required in each cycle and
𝐻𝑒𝑎𝑡 𝑒𝑛𝑔𝑖𝑛𝑒 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝑒 = = = 1− (b) the energy expelled to the hot reservoir.
𝑄ℎ 𝑄ℎ 𝑄ℎ
COP

𝑄𝑐 𝑄𝑐
𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 𝐶𝑂𝑃(𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑚𝑜𝑑𝑒) = =
𝑊 𝑄′ℎ − 𝑄𝑐

COP
𝑄′ℎ 𝑄′ℎ
𝐻𝑒𝑎𝑡 𝑝𝑢𝑚𝑝 𝐶𝑂𝑃 (ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑚𝑜𝑑𝑒) = = A cyclic process
𝑊 𝑄′ℎ − 𝑄𝑐
𝑊 = 𝑄′ℎ − 𝑄𝑐

Heat expelled = Heat removed + Work done.

46 47

Efficiency of the Otto Cycle Second Law of Thermodynamics in Terms of Entropy.

Find the thermal efficiency of an engine operating in an idealized Otto cycle. Treat the
working substance as an ideal gas. The total entropy of an isolated system that undergoes
AB : adiabatic : Q AB = 0 a change cannot decrease.
BC : isovolumetric : Q BC = nCV (TC − TB )  0
CD : adiabatic : QCD = 0
DA : isovolumetric : Q DA = nCV (TA − TD )  0 • If the process is irreversible, then the total entropy of
Q h = Q BC = nCV (TC − TB )
Q'c = −Q DA = nCV (TD − TA ) an isolated system always increases.
Q' T −T
e = 1− c = 1− D A
Qh TC − TB • In a reversible process, the total entropy of an isolated
AB : adiabatic : TV  −1 = const
TA V1 −1 = TBV2 −1 system remains constant
CD : adiabatic : TV  −1 = const
TD V1 −1 = TC V2 −1 The entropy of the Universe increases in all real processes
V1 −1 TB TC TC − TB
= = =
V2 −1 TA TD TD − TA
 −1
Q'c V 
e = 1− = 1 −  2  49
Qh  V1 

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Entropy – a measure of disorder Entropy – a measure of disorder

Entropy (microscopic definition) – Static significant of entropy Dividing the container into 2 equal sections
Each microstate is the method arranging 3 molecules in one of two
sides


 thermodynamics probability - the

number of microstates for a given
macrostate The number of microstates correspond to three molecules
distributing in two side 1= 6
The more microstates there are that
The number of microstates correspond to three molecules being in
correspond to a given macrostate, the one side 2 = 2
1> 2 Entropy of dispersion state is larger than that of clustering
greater is the entropy of that microstate.
state → molecules tend to dispersed naturally.
Entropy is a measure of disorder. 50 51

Entropy – a measure of disorder The Change in Entropy

CLAUSIUS’S INTEGRATION
CARNOT ENGINE
Two reservoirs, Divide any reversible cycle into a series of
thin Carnot cycles, where the isothermal
temperature Th, Tc P Q j, Tjprocesses are infinitesimally short:
e  e carnot
Q'c T
1−  1− c
Qh Th
Q'c T
− − c
Qh Th Qi, Ti
Qc Q
− h V
Tc Th
Q  = reversible cycle
Qh Q
+ c 0
 Ti  0  irriversible cycle
Th Tc i i 

Q  = reversible cycle
 T
 0
  irriversible cycle
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The Change in Entropy The Change in Entropy

Q  = reversible _ cycle
Q  = reversible cycle Consider an irreversible cycle
  0
  0
  irriversible cycle
1a2: irreversible T   irreversible _ cycle
P T 2b1: reversible Q
1
a
Consider a reversible cycle 1a2b1 The Clausius integration has sign “<“  T
0
The Clausius integration has sign “=“ 1a 2 b1 _ irrev.
Q P Q Q
 T +  T 0
2
 T
=0 1

b 1a 2 b1 a 1a 2irrev. 2 b1 _ rev.
Q Q Q Q
V 
1a 2
T
+ 
2 b1
T
=0 2
 T  −  T
Definition: We define a b 1a 2irr. 2 b1rev.
Q Q Q Q
state variable S that the  T
=−  T  T   T
change in the entropy dS 1a 2 2 b1 V
1a 2 _ irr. 1b 2 _ rev.
is equal to the heat Q Q Q
received in a reversible  T
=  T  T = S
process divided by the Q 1a 2 _ rever 1b 2 _ rever.
S =  Q  = reversible _ process 1− 2 rev.
absolute temperature of 1− 2 _ reversible
T S   
T   irreversible _ process Q
the system Q rev.
1− 2 S  
S is state function dS = 54
T 55
T 1a 2 _ irr.

The Change in Entropy The principle of Increase of Entropy

Q rev. Q  = reversible _ process
State _ 2
• Entropy S is a state variable S = S2 − S1 =  S   
State _ 1
T
1− 2
T   irreversible _ process
P

Q rev
1
Entropy is a state variable
a

2
• the change in entropy during a process
depends only on the endpoints
S12 =  T S may be >0; <0 or =0
12
• the change in entropy is independent
 irreversible _ process
For an isolated system dQ=0 → S12  0
b
of the actual path followed.
V Consequently, the entropy change for an = reversible _ process
S1a 2irrev. = S1b 2rev. = S12 irreversible process can be determined by
S > 0, for irreversible processes
Q calculating the entropy change for a
S12   S = 0, for reversible processes
reversible process that connects the same
1a 2
T S < 0, the process is impossible
Q initial and final states.
S12 =  T
1b 2 The entropy of the Universe increases in all real processes.
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The Change in Entropy of an Ideal Gas The Change in Entropy of an Ideal Gas
Q rev
dS = V2
T P2 V nRT ln
S = nC v ln + nCp ln 2
2
dQ Q12 V1 V2
dU = Q − PdV Isothermal Process S =  = = = nR ln
P1 V1 T T T V1
Q = dU + PdV 1

dU + PdV i nRdT nR
dS = = + dV 2
nC v dT T
T 2 T V
Iso volumetric Process S =  = nC v ln 2
T2
i nRdT
V2
nR T T1
S = 2 + dV 1
T1
T V
V
1 i
U = nRT; PV = nRT 2
nCp dT T2
T V
= nC v ln 2 + nR ln 2 2
Isobaric Process S =  = nCp ln
T1 V1 i T T1
Cv = R 1
P2 V2 V 2
= nC v ln + nR ln 2 i+2
P1V1 V1 Cp =
2
R = Cv + R Adiabatic Process S = 0 S = const
P V V Iso entropy Process
= nC v ln 2 + nC v ln 2 + nR ln 2 59 60
P1 V1 V1

The Change in Entropy of an Ideal Gas

Example Change in Entropy: Melting
A solid that has a latent heat of fusion Lf melts at a temperature Tm.
Calculate the change in entropy of this substance when a mass m of
the substance melts.
2
𝑑𝑄
Δ𝑆 = න
𝑇
1
𝑇 = 𝑇𝑚𝑒𝑙𝑡 = 𝐶𝑜𝑛𝑠𝑡
𝑄 𝑚𝐿𝑓
Δ𝑆 = =
𝑇 𝑇𝑚𝑒𝑙𝑡

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