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THERMODYNAMICS
• branch of physical science that treats various phenomena of energy and
the related properties of matter, especially of the law of transformation
THERMODYNAMICS of heat into other forms of energy and vice-versa.

Examples of everyday transformation:

• Process of converting heat into electrical work (electrical power
generation)
• Process of converting electrical work into cooling (air conditioning)
• Process of converting work into kinetic energy (automotive
transportation)
Prepared By:
Prof. Rene D. Estember

THERMODYNAMIC S YSTEM (or simply a SYSTEM) Kinds of Thermodynamic System

• refers to the quantity of matter or certain volume in space chosen for 3. Isolated System
study. • A system in which neither mass nor energy crosses the boundaries and it
is not influenced by the surroundings. (Δm = 0, W=0, Q=0)
 Surroundings - the mass or region outside the system.
 Boundary – the real or imaginary surface that separates the system PROPERTIES OF A SYSTEM
from the surroundings. The boundary of the system can either be • Any characteristic of a system is called a property.
fixed or movable.
Types of Thermodynamic Properties
Kinds of Thermodynamic System A. Static Properties
1. Closed system (also known as control mass) • refer to the physical condition of the working substance such as
• a system in which there is no transfer of matter across the boundary. It temperature, pressure, density, specific volume, specific gravity, or
consists a fixed amount of mass, and no mass can cross its boundary. relative density.
That is, no mass can enter or leave a closed system.
2. Open system (also known as control volume) B. Transport Properties
• a system in which there is a flow of matter through the boundary. It • refer to the measurement of diffusion within the working medium
usually encloses the device that involves mass flow such as resulting from molecular activity, like viscosities, thermal
compressor, turbine, or nozzle. conductivities, etc.

Conversion Formulas
Classification of Thermodynamic Properties
A. Intensive Properties
o 9
F  C  32
o
C
5
F  32
5 9
• independent of the mass such as temperature, pressure, density, and o
R  F  460
o
K  C  273
voltage.
The Temperature Interval (Change)
B. Extensive Properties • The difference between two temperature readings from the same scale,
• dependent upon the mass of the system and are total values such as total and the change in temperature through which the body is heated.
volume and total internal energy.
TK o  TC o TF o 
9
TC o
5
The State Properties
TRO  TF O
9
1. Temperature TF o  TC o
5
• An indication or degree of hotness and coldness and therefore a • Note: The degree must be written after the temperature scale for it to
measure of intensity of heat. indicate that it is a change in temperature
 Absolute temperature – the temperature measured from absolute ZEROTH LAW OF THERMODYNAMICS
zero.
• When any two bodies are in thermal equilibrium with the third body, they
 Absolute zero – the temperature at which the molecules stop are in thermal equilibrium with each other. (Note: the third body is
moving. The absolute zero equivalent to 0oK (-273.15oC) or 0oR (-
usually a thermometer)
460oF).

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2. Density (Specific Weight) 4. Pressure

 Mass density – the mass per unit volume. • The force exerted per unit area.
m where: m = mass (kgm, g, slug, lbm)  Absolute pressure - the true pressure measured above a perfect
 V = volume (m3, cm3, ft3) vacuum.
V ρ = density (kgm/m3, g/cm3, lbm/ft3) Gage Pressure
• pressure measured from the level of atmospheric pressure by most pressure
 Weight density (Specific Weight) – the weight per unit volume. recording measurement like pressure gage and open-ended manometer.
Fg V Ah ghg
  g
F where: Fg = force due to gravity /weight (kgf,N, g, lbf) p gage     h p gage  hg  ghg 
V V = volume (m3, cm3, ft3) A A A v
γ = specific weight (kgf/m3, N/m3, g/cm3, lbf/ft3) Atmospheric pressure
3. Specific Volume • pressure obtained from barometric reading.
• The volume per unit mass pabs  pgage  patm
patm  101.325kPa  760mmHg
V 1 where: m = mass (kgm, g, lbm)
v  where: pabs = absolute pressure patm  14.7 psi  1atm
m  V = volume (m3, cm3, ft3)
υ = specific volume (m3/kgm, cm3/g, ft3/lbm) pgage = gage pressure kg
patm = atmospheric pressure patm  1.032  29.92inHg
cm
()  pabs  patm dyne
patm  1.013bar  1.013x106
()  pabs  patm cm 2

Critical Pressure CONSERVATION OF ENERGY

• Minimum pressure needed to liquefy gas at its critical temperature. • The law of conservation of energy states that energy is neither created nor
destroyed.
5. Specific Gravity (Relative Density) • The fist law of Thermodynamics states that one form of energy may be
• Also known as relative density. It is the ratio of the density of a certain converted into another.
gas/substance to the density of air/water at the same temperature. Gravitational Potential Energy – is its energy due to its position or elevation.

 gas / subs  gas / subs MWgas / subs Rair P  Fg z  mgz Where: z = height
S .G.     Fg = weight
 air / water  air / water MWair / water Rgas P  P2  P1  mg ( z2  z1 ) m = mass
g = acceleration due to gravity
CONSERVATION OF MASS P = Potential energy, ΔP = change in potential energy
• The law of conservation of mass states that the mass is indestructible. Mass Kinetic Energy – the energy or stored capacity for performing work possessed
(m1) entering the system is equal to the sum of the stored mass (Δm) and by a moving body, by virtue of its momentum.
the mass (m2) that leaves the system. m 2 Where: m = mass
K υ = velocity
m1  m2 Where: A = cross sectional area of the
stream
2
K = kinetic energy
A11 1  A2 2  2 υ = average speed
m 2 2
K  K 2  K1   2  1
2
  ΔK = change in kinetic energy
ρ = density

CONSERVATION OF ENERGY CONSERVATION OF ENERGY

Internal Energy – is energy stored within the body or substance by virtue of the
activity and configuration of its molecules and of the vibration of the atoms Flow Work (Wf) – of work flow energy is work done in pushing a fluid across a
within the molecules. boundary, usually into or out of a system.
u = specific internal energy (unit mass): Δu = u2 – u1 Where: ΔWf = change in flow
U = mu = total internal energy (m mass): ΔU = U2 - U1 W  FL  pAL
f work

Work (W) – is the product of the displacement of the body and the component W f  pV
of the force in the direction of the displacement. Work is energy in
transition; that is, it exists only when a force is “moving through a W f  W f 2  W f 1  p2V2  p1V1
distance.”

• Work of a Nonflow System Heat (Q) – is energy in transit (on the move) from one body or system to
another solely because of temperature difference between the bodies or systems.
2
Work done by the system is positive (outflow of energy).
W   pdV Q is positive when heat is added to the body or system.
Work done on the system is negative (inflow of energy).
1
Q is negative when heat is rejected by the body or system.

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CONSERVATION OF ENERGY CONSERVATION OF ENERGY

Steady Flow Energy Equation Enthalpy (H, h) - is a composite property applicable to all fluids . It is the
heat energy transferred to a substance at a constant pressure process. It is
Characteristics of steady flow system defined by:
1. There is neither accumulation nor dimunition of mass within the system. h  u  pv
2. There is neither accumulation nor dimunition of energy within the system. H  mh
3. The state of the working substance at any point in the system remains
H  U  pV
constant.

Energy Entering the System = Energy Leaving the System Thus, the steady flow energy equation becomes:

P1  K1  W f 1  U1  Q  P2  K 2  W f 2  U 2  W P1  K1  H1  Q  P2  K 2  H 2  W

THE IDEAL GAS THE IDEAL GAS

• An ideal gas is ideal only in the sense that it conforms to the simple perfect
gas laws. Charles’ Law
(1) If the pressure on a particular quantity of gas is held constant, then, with
Boyle’s Law any change of state, the volume will vary directly as the absolute
• If the temperature of a given quantity of gas is held constant, the volume of temperature.
a gas varies inversely with the absolute pressure during a change of state. V T or V  CT
V1 V2
1 C V
C 
V orV  T
or T1 T2
p p
(2) If the volume of a particular quantity of gas is held constant, then, with any
pV  C change of state, the pressure will vary directly as the absolute temperature.
p T or p  CT
p1V1  p2V2
p p1 p
C or  2
T T1 T2

THE IDEAL GAS THE IDEAL GAS

Equation of State or Characteristic Equation of a Perfect Gas Equation of State or Characteristic Equation of a Perfect Gas

Combining Boyle’s and Charles’ Laws, The values of Universal Gas constant:

pV
 mR , a constant R = 8.314 kJ/moloK
T = 1545 ft. lb./mol oR
= 1.986 BTU/mol oR
pV  mRT where: p = absolute pressure
V = volume = 0.0821 L. atm/mol o K

pV  n R T v = specific volume
 m = mass Gas constant of diatomic oxygen:
R m
R  n T = absolute temperature 
8.314kJ / mol.K
M M R R(O2 ) 
R = specific gas constant or gas constant R(O2 )  = 0.2598 kJ/kg.K
 M (O2 ) 32kg / mol
= 48.28 ft.lbf/lbm.oR
pv  RT (unit mass) R = universal gas constant
n = no. of moles Gas constant for air:
M = molecular weight Rw = 0.287 kJ/kg.K = 53.34 ft.lbf/lbm.oR

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THE IDEAL GAS THE IDEAL GAS

Specific Heat Constant Volume Specific Heat (cv)

• The specific heat of a substance is defined as the quantity of heat required Qv  U
Qv  mcv T2  T1 
to change the temperature of unit mass through one degree.

Heat (energy _ units)

c
(mass)(change _ of _ temperature) Constant Pressure Specific Heat (cp)
dQ Q p  mc p T2  T1 
c or dQ = mcdT
mdT 2

And for a particular mass m, Q p  U  W  U   pdV

2 1
Q  m  cdT
1
Q p  U  pV2  V1 
If the mean or instantaneous value of specific heat is used,
2
Q p  U 2  U1  p2V2  p1V1
Q  mc  dT  mcT2  T1  Q p  H 2  H1
1

THE IDEAL GAS THE IDEAL GAS

Ratio of Specific Heats Enthalpy of an Ideal Gas

• The change of enthalpy of an ideal gas is given by the formula,
cp
k
cv
1
H  mc T  T 
p 2 1
whether the pressure remains constant or not.

Internal Energy of an Ideal Gas

• Joule’s law states that “the change of internal energy of an ideal gas is a Relations between cp and cv
function of only the temperature change.” From h = u + pv and pv = RT
dh = du + R dT
Therefore, ΔU is given by the formula,

U  mcv T2  T1  whether the volume remains constant or not. c p dT  cv dT  RdT R

cv 
c p  cv  R k 1
kR
cp 
k 1

THE IDEAL GAS THE IDEAL GAS

Entropy (S, s) Temperature – Entropy Coordinates

• Entropy is that property of a substance which remains constant (if no heat
enters or leaves the substance, while it does work or alters its volume, but dQ = TdS
which increase or diminishes should a small amount of heat enter or leave.
2
Q   TdS
• The change of entropy of a substance receiving (or delivering) heat is 1
defined by
Where: dQ = heat transferred at the temperature T
dQ Other Energy Relations
dS  ΔS = total change of entropy
T 2 2
2
dQ S  
mcdT   Vdp  Ws  K (Reversible steady flow, ΔP=0)
S  
1
T 1
T 1

2
dT T
S  mc   mc ln 2 (constant specific heat)
1
T T1

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PROCESSES OF IDEAL GAS PROCESSES OF IDEAL GAS

Constant Volume Process (Isometric Process)
Thermodynamic Processes • An isometric process is a reversible constant volume process. A constant
• Thermodynamic process is any change that a system undergoes from one volume process may be reversible or irreversible.
equilibrium state to another. It can be reversible or irreversible.
Process Formula Process Formula
 Path is the series of states through which a system passes during a
p, V, T relations T2 p2
process. 
T1 p1 n 
a) Reversible Process (Quasi-equilibrium process) 2
(Wn) 0 (reversible) Specific heat cv
• It is the process that can be reversed without leaving any trace on the 
1
pdV
Q – ΔU (irreversible) c
surroundings. That is, both the system and the surroundings are returned o
2
their initial states at the end of the process.
  Vdp (Ws) V(p1 – p2) H2 – H1 mcp(T2 – T1)
1

b) Irreversible Process
T2
• It is the process that proceed spontaneously in one direction but the other. U2 – U1 mcv(T2 – T1) S2 – S1 mcv ln
T1
Once having taken place, the process cannot reverse itself and always
results in an increase of molecular disorder.
Q mcv(T2 – T1) 

PROCESSES OF IDEAL GAS PROCESSES OF IDEAL GAS

Isobaric Process Isothermal Process
• An isobaric process is an internally reversible process of a substance during • An isothermal process is an internally reversible constant temperature
which the pressure remains constant. process of a substance.

Process Formula Process Formula Process Formula Process Formula

p, V, T relations T2 V2 p, V, T relations
 p1V1  p2V2
T1 V1 n 0 n 1
2 2

 pdV
Specific heat cp
 pdV
V
p1V1 ln 2
Specific heat 
1 P(v2 – V1)  c 1 V1  c
2 2
V2
  Vdp 0 H2 – H1 mcp(T2 – T1)   Vdp p1V1 ln H2 – H1 0
V1
1 1

T2 V2 p
U2 – U1 mcv(T2 – T1) S2 – S1 mc p ln U2 – U1 0 S2 – S1 mR ln  mR ln 1
T1 V1 p2

V2 p
p1V1 ln  mRT ln 1
Q mcp(T2 – T1)  Q
V1 p2 

PROCESSES OF IDEAL GAS PROCESSES OF IDEAL GAS

Isentropic Process Polytropic Process
• An isentropic process is a reversible adiabatic process. Adiabatic simply • A polytropic process is an internally reversible process during which
means no heat. A reversible adiabatic is one of constant entropy. pV n  C
and p1V1  p2V2
n n
Process Formula Process Formula
Process Formula Process Formula
p, V, T pV  p V
k k

p1V1n  p2V2n
1 1 2 2
relations k 1
k 1 n k p, V, T
T2  V1 
 
p 
 2
k
relations n 1
n 1 n -  to + 
T1 V2   p1  T2  V1  p  n
   2
 
p2V2  p1V1 mRT2  T1  Specific heat
2
T1 V2   p1 
 pdV 
2
p2V2  p1V1 mRT2  T1  k  n
c 0  pdV  Specific heat
1
1 k 1 k cn  cv 
1 1 n 1 n c  1  n 
k ( p2V2  p1V1 ) k (mRT2  T1 )
2 2
  Vdp  H2 – H1 mcp(T2 – T1)   Vdp n( p2V2  p1V1 ) n(mRT2  T1 )
1 k 1 k  H2 – H1 mcp(T2 – T1)
1 n 1 n
1 1

T2
U2 – U1 mcv(T2 – T1) S2 – S1 0 mcn
U2 – U1 mcv(T2 – T1) S2 – S1 T1
 
Q 0 Q mcv(T2 – T1)

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General Equation for Thermodynamic Curves OTHER DEFINITION OF TERMS

The general equation of any process is: 1) Saturation temperature

• Saturation temperature is the temperature at which liquids start to boil or
pV  C
n
the temperature at which vapors begin to condense.
• The saturation temperature of a given substance depends upon its pressure.
If • It is directly proportional to the pressure, i.e., it increases as the pressure is
n = 0 ; Isobaric process increased and decreases as the pressure is decreased.
n = 1 ; Isothermal process
n = k ; Isentropic process Examples:
n = -  to +  ; Polytropic process  Water boils at 100oC at atmospheric conditions (101.325 kPa).
n=  ; Isometric process  Water boils at 179.91oC at a pressure of 1000 kPa.
 Steam condenses at 311.06oC at 10 MPa.
Note: pVk is steeper than pV curve.  Steam condenses at 39oC at 0.0070 Mpa.

OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

2. Subcooled Liquid 4. Saturated Liquid

• A subcooled liquid is one which has a tempeature lower than the saturation • A saturated liquid is a liquid at the saturations (saturation temperature or
temperature corresponding to the existing pressure. saturation pressure) which has temperature equal to the boiling point
corresponding to the existing pressure. It is a pure liquid, i.e., it has no
Example: vapor content.
 Liquid water at 60oC and 101.325 kPa is a subcooled liquid. The saturation
temperature at 101.325 kPa is 100oC. Since the actual temperature of liquid Examples:
water of 60oC is less than 100oC, therefore, it is a subcooled liquid.  Liquid water at 100oC and 101.325 kPa.
 Liquid water at 333.90oC and 3 Mpa.
3. Compressed Liquid  Liquid water at 324.75oC and 12 Mpa.
• A compressed liquid is one which has pressure higher than the saturation
pressure corresponding to the existing temperature. 5. Vapor
• Vapor is the name given to a gaseous phase that is in contact with the liquid
Example phase, or that is in the vicinity of a state where some of it might be
 Liquid water at 110 kPa and 100oC is a compressed liquid since the actual condensed.
liquid water pressure of 110 kPa is greater than the saturation pressure of
101.325 kPa at 100oC.

OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

6. Saturated Vapor 8. Degrees of Superheat, oSH

• A saturated vapor is a vapor at the saturation conditions (saturation • The degrees of superheat is the difference between the actual temperature of
temperature and saturation pressure). It is 100% vapor, i.e., has no liquid or superheated vapor and the saturation temperature for the existing pressure.
moisture content. • In equation form:
oSH = Actual superheated temperature – t at existing pressure
sat
Examples:
 Steam (water vapor) at 100oC and 101.325 kPa. 9. Degrees Subcooled, oSB
 Steam at 212.42oC and 2 Mpa. • The degrees subcooled of a subcooled liquid is the difference between the
saturation temperature for the given pressure and the actual subcooled
7. Superheated Vapor liquid temperature.
• A superheated vapor is a vapor having a temperature higher than the • In equation form:
saturation temperature corresponding to the existing pressure. oSB = t at a given pressure – actual liquid temperature
sat

Examples:
 Steam at 200oC and 101.325 kPa. (tsat at 101.325 kPa= 100oC)
 Steam at 300oC and 5 Mpa (tsat at 5 Mpa = 263.99oC)

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OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

10. Wet Vapor 14. Critical point

• A wet vapor is a combination of saturated vapor and saturated liquid. • The critical point represents the highest pressure and highest temperature at
which liquid and vapor can coexist in equilibrium. The state of water at
11. Quality, x critical conditions whether it is saturated liquid or saturated vapor is
unknown. Hence, the latent heat of vaporization of water at this condition
• The quality of wet vapor or wet steam is the percent by weight that is is either zero or undefined.
saturated vapor.

15. Sensible Heat

12. Percent moisture, y
• Heat that causes change in temperature without a change in phase.
• The percent moisture of wet vapor is the percent by weight that is saturated
liquid.
16. Sublimation
13. Latent Heat of Vaporization • The term used to describe the process of changing solid to gas without
• The latent heat of vaporization of a pure substance is the amount of heat passing to the liquid state.
added to/removed from the substance in order to convert it from saturated
liquid/saturated vapor to saturated vapor/saturated liquid with the 17. Deposition
temperature remaining constant. It is inversely proportional to the • The reverse of sublimation. It is the process of changing gas to solid
temperature or pressure of the substance. without passing to the liquid state.

OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

18. Latent heat of fusion 21. Dalton’s Law of Partial Pressure

• It is the heat needed by the body to change from solid to liquid without • The pressure exerted in a vessel by a mixture of gases is equal to the sum of
changing is temperature. the pressures that each separate gas would exert if it alone occupied the
whole volume of the vessel.
19. Second Law of Thermodynamics
• Heat cannot be transferred from cold body to a hot body without an input of 22. Avogadro’s Law
work. It similarly states that heat cannot be converted 100% into work. • At equal volume, at the same temperature and pressure conditions, the
The bottom line is that an engine must operate between a hot and a cold gases contain the same number of molecules.
reservoir. Also indicated is that energy has different levels of potential to
do work, and that energy cannot naturally move from realm of lower
potential to a realm of higher potential. 23. The Carnot Cycle
• The Carnot Cycle is the most efficient cycle conceivable. It consists of two
isothermal processes and two isentropic processes.
20. Third law of Thermodynamics
• The total entropy of pure substances approached zero as the absolute 24. Mean effective pressure
thermodynamic temperature approaches zero.
• It is the average constant pressure that, acting through one stroke, will do
on the piston the net work of a single stroke.

OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

25. Expansion ratio 29. Heat engine or thermal engine

• The ratio between the volume at the end of expansion and the volume at the • It is a closed system (no mass crosses its boundaries) that exchanges only
beginning of expansion. heat and work with its surrounding and that operates in cycle.

26. Compression ratio 30. Elements of a thermodynamic heat engine with a fluid as the working
• The ratio between the volume at the beginnign of compression and the substance:
volume at the end of compression.  A working substance, matter that receives heat, rejects heat, and does
work;
 A source of heat (also called a hot body, a heat resevoir, or just source),
27. Internal Combustion Engine
from which the working substance receives heat;
• It is a heat engine deriving its power from the energy liberated by the
 A heat sink (also called receiver, a cold body, or ject sink), to which the
explosion of a mixture of some hydrocarbon, in gaseous or evaporated
working substance can reject heat; and
form, with atmospheric air.
 An engine, wherein the woking substance may do work or have work
done on it.
28. Four-stroke cycle
• The four-stroke cycle is one wherein four strokes of the piston, two
revolutions, are required to complete the cycle.

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OTHER DEFINITION OF TERMS OTHER DEFINITION OF TERMS

31. Thermodynamic cycle 36. Compression-Ignition Engine

• It occurs when the working fluid of a system experiences a number of • It is also referred to as diesel engine.
processes that eventually return the fluid to its initial state.

32. Available energy

• It is that part of the heat that was converted into mechanical work.

33. Unavailable energy

• It is the remainder of the heat that had to be rejected into the receiver (sink).

34. Otto Cycle

• It is the ideal prototype of spark-ignition engine.

35. Spark-Ignition engine

• I is also referred to as gasoline engine.

SAMPLE PROBLEMS SAMPLE PROBLEMS

1. In an experiment to determine the specific heat of copper, a piece of copper 5. In the process where the product of pressure and volume is constant, a gas
weighing 50 g is first heated to 100oC in steam. It is then immersed into water at compression is carried out from an initial pressure of 200 kPa to a final pressure of
27oC. The water in the calorimeter weighs 100 g and the inner aluminium cap 800 kPa. Considering that the initial specific volume is 0.10 m3/kg, determine the
weighs 50 g. If the final temperature is 30oC, what is the specific heat of copper? work done per kilogram of gas.
Specific heat of aluminium is 0.22 cal/goC.
6. A steady state device has the following conditions of the working substance at the
2. AT STP the density of chlorine is 3.22 kg/m3. What is the weight of this gas entrance: pressure equals 100 psia and density is 62.4 lbm/ft3. If 10,000 ft3/min of
contained in a flask of 100 cubic centimetres at 24oC and 100kPa? this fluid enters the system, determine the exit velocity if the exit area is 2 ft3.

3.. A closed vessel contains air at a pressure of 160 kN/m2 gauge and temperature of 7. The volumetric flow rate of standard air is 120 m3/s at dry bulb temperature of
30oC. The air is heated at constant volume to 60oC with the atmospheric pressure of 18oC. Compute the standard air volume considering that standard air pressure is
759 mm Hg. What is the final gage pressure. 101.325 kPa and standard air temperature at 21.11oC.

4. Ammonia weighing 22 kg is confined inside a cylinder equipped with a piston has 8. A sealed tank contains oxygen at 27oC at a pressure of 2 atm. If the temperature
an initial pressure of 413 kPa at 38oC. If 2900 kJ of heat is added to the ammonia increases to 100oC, what will be the pressure inside the tank?
until its pressure and temperature are 413 kPa and 100oC, respectively. What is the
amount of work done by the fluid in kJ? (Note: Molecular Weight of NH 3 = 17). 9. What horsepower is required to isothermally compress 800 ft3 of air per minute
from 14.7 psia to 120 psia?

SAMPLE PROBLEMS

10. Two pounds of air initially at 60 psia and 600oF expands isentropically until the
temperature is 200oF. Compute the work done by the gas.

11. For a certain gas, R = 0.277kJ/kg.K and k = 1.384. a) What are the value of cp and
cv? b) What mass of this gas would occupy a volume of 0.425 cu m at 517.11 kPa
and 26.7oC? c) If 31.65 kJ are transferred to this gas at constant volume in (b), what
are the resulting temperature and pressure?