Thermodynamics

Engr. Reynaldo P. Roca

Thermodynamics- a branch of physical sciences that treats of various phenomena
of energy and the related properties of matter, especially of the laws of
transformation of heat into other forms of energy and vice versa.

Thermodynamics is the study of processes in which energy is transferred as heat

and as work.
Heat is the transfer of energy due to temperature difference; work is a transfer of
energy NOT due to a temperature difference.

Definitions

1. Fluid - a working substance that exists , or is regarded as existing , as a

continuum characterized by low resistance to flow and the tendency to
assume the shape of its container.( Steam in steam turbine, air in air
compressor, air and fuel air mixture in ICE).
2. Pure substance - one that is homogeneous in composition and homogeneous
and invariable in chemical aggregation.
3. System- the part of the universe that we choose to study.It is a region enclosed
by specific boundaries, which may be imaginary, either fixed or moving.

4. Surroundings - contain systems, some of which may affect the particular

system under study, such as source of heat.
5. Boundary- the surface dividing the system from the surroundings.
6. Systems can be:
Open: Mass and Energy can transfer between the System and the Surroundings
Closed: Energy can transfer between the System and the Surroundings, but NOT mass
Isolated: Neither Mass nor Energy can transfer between the System and the Surroundings

7. Two classes of properties

Intensive properties- have values that are independent of the size of the mass of the
system
( ex. Pressure, temp., density)
Extensive properties- dependent of upon the mass of the system and are total values
- if its values for the whole system is the sum of its values for the various subsystem or
parts ( total volume, total internal energy)
8. The Zeroth law of thermodynamics.
If system A is in thermal equilibrium with system B, and system B is in thermal equilibrium
with system C, then system A is in thermal equilibrium with system C.
Importance: This gives rise to the idea of temperature. A, B, C are at the same
temperature
System of Units

Newton’s second law of motion states that “ the acceleration of a particular body is
directly proportional to the resultant force acting on it and inversely proportional to its
mass.”

a  F ; a = kF
m m

F = ma
K
Where: k is proportionality constant
F = force
m = mass
a = acceleration

Systems of units where k is unity but not dimensionless:

cgs system: 1 dyne force accelerates 1 gm mass at 1 cm/s2

mks system: 1 newton force accelerates 1 kg forcee at 1 m/s2
fps system: 1 lb force accelerates 1 slug mass at 1 ft/s2

Systems of units where k is not unity:

If the same word is used for both mass and force in a given system, k is neither
unity nor dimensionless.

1 lb force accelerates a lb of mass at 32.174 ft/s2

1 gm force accelerates a gm of mass at 980.66 cm/s2
1 kg force accelerates a 1 kg mass at 9.8066 m/s2
Mass and Weight

The mass of a body is the absolute quantity of matter in it.

The weight of a body means the force of gravity Fg on the body.

m = F = Fg
k a g

Density() - mass of a substance per unit volume.

= m
V

Specific Volume () - is the volume of a unit mass.

= V= 1
m 
Specific Weight ()- the force of gravity of any substance on unit volume.

 = Fg
V
= g
k
Pressure

The standard reference atmospheric pressure is 760 mm Hg , 101325 Pa, 14.696

psi or 1 atm.

Measuring Pressure

By using Manometers

a. Absolute pressure is greater than atmospheric pressure.

P = Po + Pg

b. Absolute pressure is less than atmospheric pressure.

P = Po - Pg

The gage reading is called vacuum pressure or the vacuum.

Gage Pressure
Open to atmosphere

Fg

P = Po + Pg

Pg = gh
Temperature

t 0F = 9 t 0C + 32
5

t 0C = 5 (t 0F - 32 )
9

Absolute temperature is the temperature measured from absolute zero.

Absolute zero temperature is the temperature at which all molecular motion ceases, and will be
denoted by T, thus

T (0R) = t 0F + 460, degrees Rankine

T (K) = t 0C + 273, Kelvin
Conservation of Mass

The mass per unit time of fluid crossing an area A

perpendicular to velocity V is given by the formula:
m = A

The quantity of fluid passing through a given section is :

V = A
Where:
V = volume flow rate
m = mass flow rate

The law of conservation of mass states that mass is

indestructible. Hence

m1 = m2
1A11 = 2A22
Problems

1. A body which has a mass of 7.0 kg is accelerated at a rate of 3.0 m/s2. What total
force is required if a) the body is moving along a horizontal frictionless plane? b) the
body is moving vertically upward at a location where local gravity is 9.45 m/s2?
2. On the surface of the moon where local gravity g is 1.67 m/s2, 4.4 kg of a gas occupy
a volume of 1.2 m3 . Determine a) the specific volume of the gas,in m3/kg;b) density
in g/cm3; and c) specific weight in N/m3..
3. If the barometer reads 735 mmHg, determine what absolute pressure, in bars, is
equivalent to a vacuum of 280 mmHg within a system. Neglect the effect of
temperature on the density of mercury.
4. A manometer is used to measure the pressure in a tank.The fluid is an oil with a
specific gravity of 0.87, and the liquid height is 45.2cm.If the barometric pressure is
98.4KPa,determine the absolute pressure within the tank, in KPa and Atmospehe if
g= 9.78m/s2 .

5. If a pump discharges 284 lpm of water whose density is 985 kg/m3 , find a) the mass
flow rate (kg/min) b) the total time required to fill a vertical cylinder tank 3.05 in
diameter and 3.05m high.
Conservation of Energy

Gravitational Potential Energy(P)

The gravitational potential energy of a body is its energy due to its position or
elevation.

Fg
Z
P = FgZ = m g z
K
P = P2 – P1 = mg(Z2 – Z1)
K

Kinetic Energy (K)

The energy or stored capacity for performing work possessed by moving body, by virtue of its
momentum.

K = mv2
2k

k = m(v2 2 – v1 2)
2k
Internal Energy ( U,u)

Internal energy is stored within a body or substance by

virtue of the activity and configuration of its molecules and of the
vibration of the atoms within the molecules.

u = specific internal energy ( unit mass)

u = u2 - u2

U = total internal energy

U = U2 – U1

For Ideal gas

dU =Cv dT Always for ideal gas ;U(T) only depends on T
The internal energy of an ideal gas depends only on temperature

Work (Wn)

Work is the product of the displacement of the body and the

component of the force in the direction of the displacement.
Cylinder Final Position of Piston

Piston

Area=A

Piston Rod

P V2
1

V1 dw

c f

dW 2
P
dV

m nV

dw = Fd = (pA) = pdV

W = ∫1 pdV work done during a nonflow reversible process.

Work done by the system is positive ( outflow of energy).

Work done on the system is negative (inflow of energy).
Flow work (Wf)

Flow work or flow energy is work done in pushing a fluid across a boundary, usually into or out of
a system.

Boundary
A= Area of Surface System
p
F V

c L

Heat (Q)

Heat is energy in transit (on the move) from one body or system to another solely because of a
temperature difference between the bodies or system.
That quantity flowing between the system and the surroundings that can be used to change the
temperature of the system and/or the surroundings .
Heat (q), like w, is a function of path. Not a state function .It is possible to have a change of state

(p1, V1, T1) = (p2, V2, T2)

adiabatically (without heat transferred)

Q is positive when heat is added to the body or system.

Q is negative when heat is rejected by the body or system.
Let us consider a control mass undergoing a quasi-
equilibrium constant-pressure process, as shown below.
[ specific enthalpy, h, and total enthalpy, H. ]
The First Law is often called the conservation of energy
law.
The first law of thermodynamics states that during any
cycle a system (control mass) undergoes, the cyclic
integral of the heat is proportional to the cyclic integral of
the work.
First Law of Thermodynamics: (Energy Conservation)
The change in a stationary object’s internal energy
is equal to the heat transferred into that object minus the work
that object did on its surroundings.
Work
U = Q - W
done W

piston
U

Gas
Molecules
at temp T

Q
candle

Internal Energy U – measure of thermal energy of system

Heat in – heat added to system
Work done – work done by the system
The energy of a closed system can only be changed through heat and work
interactions.

Conservation of Energy

The law of conservation of energy states that energy is neither

created nor destroyed.

The first law of thermodynamics states that one form of energy

maybe converted into another.

The total energy of the universe is constant .Heat, work, and other
energy transfers in an event equal the total energy content both before and
after the event has occurred
Steady flow energy Equation

P1 1 W

System

K1 1
p1 V1 Q P2

U1 P2

z1 p2V2
U2 z2

Datum Level 6

Energy Entering System = Energy Leaving the System

P1 + K1 + Wf1 + U1 + Q = P2 + K2 + Wf2 + U2 + W

Q = ∆P + ∆K + ∆Wf + W

Enthalpy(H,h)

Enthalpy is a composite property applicable to all fluids.

H = u + pv and H = mh = U + PV

Steady flow energy equations becomes:

P 1 + K1 + H1 + Q = P 2 + K 2 + H 2 + W

Q = ∆P + ∆K + ∆H + W
Problems:
1. A girl weighing 470N hangs suspended on the end of the rope 8m long.What will be
her gain in potential energy when a friend swings her to one side so that the rope
makes an angle of 350 with the vertical ? If local g = 9.7 m/sec2 , what is her mass in
Kg?
2. If 6 l of a gas at a pressure of 100KPaa are compressed reversibly according to PV2
=C until the voule becomes 2l, find the final pressure and the work.
3. An 8.0 Kg mass moves at 30.0 m/s.What is its kinetic energy? If the object was
initially at rest ,how much work was done on the object to give its kinetic energy?
4. The 600Kg hammer of a pile driver is lifted 2m above a filing head. What is the
change in potential energy?If the hammer is released ,what will be its velocity at the
instant it strikes
5. During a reversible process executed by a nonflow system, the pressure increases
from 344.74 Kpaa to 1378.96 Kpaa in accordance with PV= C, and the internal
energy increases 22,577 J; the initial volume is V1 = 85l. Find the heat.
6. An internally reversible process occurs in a system during which Q = -12 KJ,
U= -79 KJ, and H = -111KJ. A) Find the work if the system is nonflow. b) determine
the shaft work and the change of flow energy if the system is steady-state steady flow
with K = 4KJ.c) using the conditions stated in b) evaluate ∫ pdv and -∫ vdp
in KJ.
7. A piston cylinder device contains air initially at 6 bars ,177deg Celsius and 0.05m3 .
The gas undergoes a process according to the equation PV2 =C . The final pressure is
1.5 bars. Determine the a) the work done, in Nm and b) the change in internal energy
in KJ if the heat input is 5.0KJ.
8. A compressor draws 500cfmof air whose density is 0.079lb/ft3 and discharges it with
a density of 0.304lb/ft3 . At the suction ,p1 =15psia; at the discharge ,p2= 80psia.The
increase in specific internal energy is 33.8Btu/lb, and the heat from the air by cooling
is 13Btu/lb. Neglecting change of potential and kinetic energy , determine the work
done on the air in Btu/min and Hp.
Ideal Gas

An ideal gas is ideal only in the sense that it conforms to the simple perfect gas laws
Boyle’s Law

If the temperature of a given quantity of gas is held constant, the volume of the gas varies
inversely with the absolute pressure during a change of state.

V α 1 or V = 1
p P

PV = C or P1V1 = P2V2

Charles

1. If the pressure on a particular quantity of gas is held constant then, with any change in state, the
volume will vary directly as the absolute temperature.

V α T or V = CT

V =C
T

2. If the volume of particular quantity of gas is held constant, then, with any change of state , the pressure
will vary directly as the absolute temperature.

P α T or P = CT

P =C
T
Equation of State

P1 V 1 = P2 V 2
T1 T2

PV = C
T

PV = R
T

Where: P= absolute pressure

V = volume
m = mass
T = absolute temperature
R = specific gas constant

Entropy- property of a substance which remains constant if no heat enters or leave the substance while it
does work or alters its volume, but which increases or diminishes should a small amount of heat enters or
leave.

ds = dQ/T or S =  dQ/T

or S= mclnT2/T1
1. For a certain ideal gas, R = 0.277 KJ/kg-K and K= 1.384. a) what are the
values of cp and cv? b) what mass of this gas would occupy a volume of 0.425
m3 at 517.11Kpa and
26.7 0C? If 31.65 KJ are transferred to this gas at constant volume in b) what
are the resulting temperature and pressure?
2. The temperature of an ideal gas remains constant while the absolute
pressure changes from 103.4 Kpaa to 827.2 Kpaa. a) If the initial volume is 80
l, what is the final volume? For 160g of the gas determine the change of
density expressed as a percentage of the initial density.
3. A balloon is filled with methane (CH4) at 20 deg Celsius and 1 bar until the
volume is 26.5 m3 .
Calculate the mass of gas, in Kg , in the balloon
Determine the volume , in cubic meters, if the balloon rises to a height where
the state is 0.84 bar and 00 C.
Processes of Ideal Gases

Reversible and Irreversible Process

A process commencing from an initial equilibrium state is called totally
reversible if at any time during the process both the system and the environment
with which it interacts can be returned to their initial states.

An overall process is irreversible if either the system or its surroundings cannot be

returned to their initial states.
• Identify
the direction of a process. (ex: Heat can only transfer from a hot object to a
cold object, not the other around)

• Can be used to determine the “Quality” of the energy. (ex: A high-temperature energy
source has a higher quality since it is easier to extract energy from it to deliver useable
work.)

•Can be used to exclude the possibilities of constructing 100% efficient heat engine and
any perpetual-motion machines. (Kevin-Planck statement and Clausius statement)

• Reversible processes and irreversibilities.

• Determine the theoretical limits for the performance of engineering systems. (ex: A
Carnot engine is theoretically the most efficient heat engine and its performance can be
used to set as a standard for other practical machines)
 Disorder vs Order – the meaning of entropy
Entropy – a measure of the disorder of a system

ORDER
(small entropy)

DISORDER
(large entropy)

ORDER to DISORDER: Statistically Likely to happen

Reverse….. Very rarely happens
Converting Thermal Energy to Ordered Energy is rare
 Second Law of Thermodynamics
The entropy of a thermally isolated system of objects
never decreases.

What does this mean ?

Let represent molecules of a COLD gas
and represent molecules of a HOT gas

Which of the following events are likely to happen ?

A.

B.

Natural Flow of Heat is from HOT to COLD !

• A process can not happen unless it satisfies both the first and second laws of
thermodynamics. The first law characterizes the balance of energy which defines the
“quantity” of energy. The second law defines the direction which the process can take
place and its “quality”.

• Define a “Heat Engine”: A device that converts heat energy into work while operating in
a cycle. Ex: A steam power plant.

Q-Wnet=U, U=0 for a cycle

Wnet=QH-QL
Thermal efficiency
hth=Wnet/QH=(QH-QL)/QH
TH =1-(QL/QH)

QH Question: Can we produce an 100% heat engine?

QL=0?

Heat engine Wnet

QL
TL
• It
is impossible for any device that operates on a cycle to receive heat from a single
reservoir and produces a net amount of work.
• This is a statement without proof, but has not been disproved yet.
• Therefore, the question from previous slide is “NO”. It is not possible to built a heat
engine that is 100%.

• A heat engine has to reject some energy into

a lower temperature sink in order to complete
the cycle.
• TH>TL in order to operate the engine.
TH Therefore, the higher the temperature, the
higher the quality of the energy source since it
can produce useable work to more lower-
QH temperature energy sinks.

Heat engine

Wnet
• A “heat pump” is defined as a device that transfers heat from a low-temperature source
to a high-temperature one. Ex: a heat pump to extract energy from outside cold outdoor air
into the warm indoors.

• Coefficient of Performance (COP): COP=QH/Wnet=QH/(QH-QL)

= 1/(1-QL/QH)

TH • COP>1, ex: a typical heat pump has a COP in the order of 3

• Question: can we built a heat pump operating at , that is Wnet=0? QH=QL?

QH

Heat pump Wnet

QL
TL
• Itis impossible to construct a device that operates in a cycle and produces no effect other
than the transfer of heat from a lower-temperature body to a higher-temperature body.
• Also can not be proved, rather depends on experimental observations.
• Heat can not transfer from low temperature to higher temperature unless external work
is added.

• Therefore,
it is not possible to built a heat
TH pump without external work input.
QH

Heat pump

QL
TL
 • It
can be shown that the violation of the one statement means the violation of the other statement.
They are equivalent.

100% heat engine: against K-P Statement

TH
QL
TH

QH QH+QL
Heat pump

QL
Heat engine Heat pump
TL
Wnet
=QH
QL

Heat transfer from low-temp body to high-

temp body without work- violation of the C-
TL
statement
• A reversible process means there are no irreversibilities exist when a system is
undergoing interaction with its surroundings. Therefore, the process can be
reversed without leaving any trace on its surroundings. Both system and the
surroundings are returned to their initial states. It is an ideal process that can not
happen in reality. However, if the irreversibilities are small enough, some
processes can be approximated as reversible. Ex: a frictionless pendulum, quasi-
equilibrium expansion and compression of gas in a cylinder/piston assembly (in
an idealized Carnot cycle)

• Irreversibilities: friction, sudden expansion and compression, heat transfer

between two bodies with finite temperature difference.
Other statements of the 2nd law include
• No heat pump can transfer thermal energy from a low temperature
to a higher temperature reservoir without work being done on it
(Clausius)
• The entropy of the universe can never decrease

• Entropy
» This is a measure of the disorder of a system
» Most systems, when left, tend towards more disorder
» This is why heat spreads from hot to cold.
» Entropy can decrease in a small part of a system

36
» The 2nd Law was “discovered” by Clausius from numerous observations showing
that if a process is reversible, is path-independent.

» Any quantity whose change is independent of the path must be a

thermodynamic property .
» Clausius called the property entropy, with the symbol S:

2 2


 Q rev 

Q 
d  S 2  S1  d  rev 
 T   T 
1 1

37
» For irreversible processes, the equality no longer holds. Instead:
2


Q
S 2  S1  d 
T
1
In irreversible processes, entropy is created!

38
Changes that happen during a thermodynamic process can usefully
be shown on a pV diagram

39

V
 The area under the graph represents the work done

This area represents the work

done by the gas (on the
surroundings) when it
expands from state A to state
B
B

V 40

What happens if the gas is going from state B to A?

 These take place at constant volume
1.V = constant, so p/T = constant
2. Non-flow work = ʃpdv =0
p
3. The change in internal energy ,∆U = mCv(T2 –T1 )
A
4. The heat transferred ,Q = mCv(T2 –T1 )
5. The Change in Enthalpy, ,∆H= mCp(T2 –T1 )
5. The change of entropy, ∆S= mCvln( T2/T1)
6. Reversible steady flow consttant volume,Wsf
B Wsf = _(∆Wf + ∆K+ ∆P)

41
 These take place at constant pressure
1. p = constant, so V/T = constant
2. Non-flow work = ʃpdv =p(V2-V1)
3. The change in internal energy ,∆U = mCv(T2 –T1 )
p 4. The heat transferred ,Q = mCp(T2 –T1 )
5. The Change in Enthalpy, ,∆H= mCp(T2 –T1 )
A B
5. The change of entropy, ∆S= mCpln (T2/T1)
6. Reversible steady flow consttant volume,Wsf
Wsf = _( ∆K+ ∆P)

Isobaric
expansion 42
 These take place at constant temperature

A 1. T = constant, so pV = constant
p 2. Non-flow work = ʃpdv =p1V1lnV2/V1
3. The change in internal energy ,∆U = 0
4. The heat transferred ,Q = p1V1lnV2/V1
5. The Change in Enthalpy, ,∆H= 0
B
5. The change of entropy, ∆S= Q/T=mRln( P1/P2)
6. Reversible steady flow consttant volume,Wsf
Wsf = Q_( ∆K+ ∆P)
V
Isothermal
expansion
43
 No thermal energy transfer with the surroundings
A (approximately a rapid expansion or contraction)
1. P1V1 K = P2V2K
p T2/T1 = (V1/V2)K-1
T2/T1 = (P2/P1)K-1/k
2. Non-flow work = ʃpdv =(p2V2-p1V1)/1-k
3. The change in internal energy ,∆U = mCv(T2 –T1 )
4. The heat transferred ,Q = 0
B
5. The Change in Enthalpy, ,∆H= mCp(T2 –T1 )
5. The change of entropy, ∆S= 0
6. Reversible steady flow isentropic ,Wsf
Wsf = Q_( ∆K+ ∆P+∆H)
V

Adiabatic
expansion 44
Problems.

1. A reversible nonflow constant volume process decreases the internal energy of 316.5
KJ for 2.268 kg of a gas for which R= 430 J/kg-K and k= 1.35. For the process
determine a) the work b) the heat c) the change of entropy if the initial temp. is
204.4C.
2. A certain gas , with cp= 0.529 Btu/lb-R , R= 96.2 ft.lb/lb R expands from 5 cu ft. and
80 F to 15 cu ft while the pressure remains constant at 15.5 psia. Compute a) T 2 b)
H c) U d) S e) For an internally reversible nonflow process, what is the work?
3. During an isothermal process at 88 F, the pressure on 8 lb of air drops from 80 psia to
5 psig. For an internally reversible process, determine a) the  pdv and the work of a
nonflow process
b) the -  vdp and the work of a steady flow process during which k = 0 c) Q d) ) U e) ) H and e) ) S

4. Find the minimum work done per Kg of air in a cycle according to the following
processes:
a. Isothermal expansion from state 1 to state 2.
b. Constant volume compression from state 2 to state 3.
c. Constant pressure compression from state 3 to the initial state.

Data: P1= 350 KPa

V1 = 1 m3 /Kg
T3 = 16500 C
d. Represent the work on a p-V diagram.
5. A piston-cylinder device contains 0.2 Kg of air initially at 100KPa and 300K . The air
is compressed reversibly and isothermally until the volume is reduced by one-half.
Determine the work transfer during this process. Sketch the p-V diagram of the
process indicating the temperature, processes, and volume at the end of points.
6. Air at a temperature of 500 0C is compressed ata constant pressure of 1.2MPa from a
volume of 2 m3 to a volume of 0.4m3 . If the initial internal energy decrease is 4820
KJ, find
a. The work done during the reversible compression
b. The heat transferred
c. The change of enthalpy