Introduction to Thermodynamics II.

Thermodynamic Properties and Quantities

Dimension and Units
Topics:  Fundamental Dimensions – primitives
I. Thermodynamics and its History  Derived Dimensions – combination of
II. Thermodynamic Properties and Quantities fundamental dimensions
III. Thermodynamic Systems
IV. State and Path Functions ღ System of Units
V. Zeroth Law - English Engineering Systems – used in
US
I. Thermodynamics and its History - International System (le Systeme
Thermodynamics International) or Metric SI System –
- from the Greek word “therme” meter-kilogram-second/mks,
(heat) and “dynamis” (power) centimeter-gram-second/cgs
- science of storage, transformation
and transfer of energy Fundamental SI Units: kg, m, s, K, A, mol, Cd
st
1 Law: Energy is conserved, thus, it is
neither created nor destroyed. Expression Some SI and English Units
of the conservation of energy principle. o Force: F = ma ; unit: N or kg*m/s 2
2nd Law: Energy has quality as well as o Weight: W = mg ; unit: N or kg*m/s2
quantity, and actual processes occur in the o Work: W = Fd ; unit: J or N*m
direction of decreasing quality of energy. o Heat /Energy: unit: 1 cal = 4.1868 J ; 1
Btu = 1.0551 kJ
ღ History of Thermodynamics
Physics of Temperature/Heat > Steam Engine > ღ Dimensional Homogeneity
Carnot Engine > Thermodynamics - All equations must be dimensionally
homogeneous
ღ Approaches In Thermodynamics - To be dimensionally homogeneous,
1. Macroscopic Approach (Classical all the terms in an equation must
Thermodynamics) – structure of matter have the same dimensions
is not considered; a few variables are - secondary units can be formed by
used to describe the state of the matter combinations of primary units or as
under consideration; the values of unity conversion ratios
these variables are measurable
following the available techniques of Example: Force can be expressed
experimental physics as:
2. Microscopic Approach (Statistical m
Thermodynamics) – knowledge of the
N=kg ∙
s2
molecular structure of matter under ft
consideration is essential; a large lb f =32.174 lb m 2
s
number of variables are needed for a
which also equates to
specification of the state of the matter
N
=1
m
ღ Application of Thermodynamics kg ∙ 2
 Automobile, refrigeration systems, air- s
conditioning systems, industrial
lb f
=1
blowers, industrial gas compressors, ft
32.174 lb m 2
industrial heat exchangers, power s
plants, renewable energy
ღ Measures of Amount or Size
 Mass (m) and Number of Moles (n)
o m and n – primitive without
definition, may be divided by
 the molar mass M, to yield  Absolute Zero – coldest temperature at
number of moles which all molecular motion is zero and all
the substance is perfectly ordered.

 Total Volume, V
o Representing the size of the
system, is a defined quantity
given as the product of three ღ Absolute Zero
lengths. It may be divided by
the mass or number of moles of
the system to yield specific or
molar volume

ღ Force
- product of mass and acceleration;
derived from Newton’s second
law: F = ma
- SI Unit: Newton, N = kg m/s2
- English Unit: Pound-force, lbf
(force which accelerates 1 lb mass Graph of Pressure Versus Temperature – kept
32.174 feet per second per at a constant volume for various gases. Note
second. that all of the graphs extrapolate to zero
pressure at the same temperature
ღ Temperature
- Degree of hotness or coldness ღ Phase Diagram of Water
of body or control volume
- Property that indicates the
direction of the flow of energy
through a thermally conducting
rigid wall.
- Measure of the average
amount of energy of motion, or
kinetic energy a system
contains

o Conversions:
t ( ° C ) =T ( K )−273.15 *Triple Point – the unique temperature and
t ( R )=1.8 T ( K ) pressure at which the solid, the liquid and gas
t ( ° F ) =T ( R )−459.67 phases of a substance are all in equilibrium
t ( ° F ) =1.8 t ( °C ) +32 (273.16 K and 0.01°C)

Phase Diagram of Water – the green lines mark

the freezing point, and the blue line marks the
boiling point, showing how they vary with
pressure. The dotted line illustrates the
anomalous behavior of water. Note that water
changes states based on the pressure and
temperature.

International Temperature Scale of 1990

 Steam Point – the boiling point of water (ITS-90)
 Ice Point – the freezing point of water
 - Used for calibration of scientific and
industrial instruments
- Based on assigned values of
temperature for a number of
reproducible phase-equilibrium
states of pure substances (fixed
points) and on standard
instruments calibrated at these
temperatures
- The platinum-resistance
thermometer is an example of F mg Ahρg
standard instrument; it is used for P= = = =ρgh
A A A
temperatures from 13.8 K (-259.35
C) (the triple point of hydrogen) to  Absolute Pressure – the actual pressure at
1234.93 K (961.78 C) (the triple given position; measured relative to
point of silver). absolute vacuum
 Gage Pressure – the difference between the
ღ Pressure absolute pressure and the local
- Normal force exerted by the fluid atmospheric pressure and is thus, zero
per unit area of the surface when the pressure is the same as
- Units: SI – N/m2 or Pascal (Pa); atmospheric pressure
lbf/in2 English - psi  Vacuum Pressure – pressures below
atmospheric pressure
o The primary standard for pressure
measurement is the dead-weight
gauge in which a known force is
balanced by a fluid pressure acting
on a known area

o Manometer – used to measure

small and moderate pressure
differences; contains one or more
fluid

F mg
P= =
A A In a stacked-up fluid
layers, the pressure
o Since a vertical column of a given change across a fluid
fluid under the influence of gravity layer of density ρ
exerts a pressure at its base in and the height h is
direct proportion to its height, ρgh.
pressure is also expressed as the
equivalent height of a fluid column.

Patm + ρ1 g h1 + ρ2 g h2 + ρ3 g h 3=P1
 A typical hydraulic system with two fluid-filled
cylinders, capped with pistons and connected by a
tube called a hydraulic line. A downward force F1
on the left piston creates a pressure that is
transmitted undiminished to all parts of the
enclosed fluid. This results in an upward force F2 on
the right piston that is larger than F1 because the
Basic Manometer right piston has a larger area.
P=P1 =P2 F 1 F2 F2 A 2
P1=P2 → = → =
P2=Patm + ρgh A 1 A 2 F1 A1

Measuring the A2
pressure drop across The area ratio is called the ideal mechanical
A1
a flow section or a advantage of the hydraulic lift.
flow device by a
differential Example 1.2
manometer A dead-weight gauge with a piston
diameter of 1 cm is used for the accurate
measurement of pressure. If a mass of 6.14 kg
(including piston and pan) brings it into balance,
P1 + ρ1 g ( a+ h )− ρ2 gh− ρ3 ga=P2 and if g = 9.82 m·s−2, what is the gauge pressure
being measured? For a barometric pressure of
o Atmospheric pressure – measured 0.997 bar, what is the absolute pressure?
by a device called a barometer;
often referred to as the barometric
pressure.
o Barometer – Used to measure
absolute pressure

PB =PC + ρgh but PC =0 (i.e. vacuum)

∴ P B= ρgh

o Pascal’s Principle:
 Total pressure in a fluid is the sum
of the pressures from different
sources.
 A change in pressure applied to an
enclosed fluid is transmitted
undiminished to all portions of the
fluid and to the walls of its
container.
Example 1.3 III. Thermodynamic Systems
A gas is Systems VS Surroundings
contained in a  Surroundings/Environment– everything
vertical, frictionless external to the system
piston cylinder  System – separated from the
device. The piston surroundings by the system boundary
has a mass of 4kg (may be fixed or flexible).
and cross-sectional
area of 35 cm2. A
compressed spring
above the piston
exerts a force of
60N on the piston.
If the atmospheric pressure is 95kPa, determine the
pressure inside the cylinder.
g = 9.81 m/s2

ღ Classification of Systems
o Closed System – have energy transfer
but no mass transfer

o Open System – have both mass and

energy transfer
 o Isolated System – neither have mass nor  State Function
energy transfer – Does not rely on the past
history of the substance nor on
the means by which it reaches a
given state
– Condition of a system identified
by properties
– P, V, T, U, H, S, A
P2 V2

∫ dP=P2−P1 =∆ P ,∫ d V =V 2−V 1=∆ V

P1 V1
ღ Properties of a System
o Behavior of a Thermodynamic System
 Path Function
 The behavior of the system
– Account for energy changes
depends upon the interaction of
occur in the surrounding
energy with or without mass
– Series of states through which a
transfer across the boundary.
system passes during process
◊ 8 Properties Describing the
– Q, W
Behavior of a System
1. Pressure (P) ∫ dQ=Q∫ d W =W
2. Temperature (T)
3. Volume (V) ღ State and Equilibrium
4. Entropy (S)  A substance can be at various
5. Internal Energy (U) pressures & temperatures or in various
6. Enthalpy (H) states
7. Gibbs Function (G) ◊ Thermal Equilibrium: temperature
8. Helmholtz Functions (H) of system does not change when it
is isolated from surroundings
◊ Mechanical Equilibrium: pressure of
system does not change when it is
isolated from surroundings
◊ Chemical Equilibrium: chemical
composition does not change when
it is isolated from surroundings
◊ Phase Equilibrium: mass of each
phrase reaches an equilibrium level
and stays there

o Thermodynamic Properties
 Intensive Properties – physical
property of a system that does
not depend on the system size
or the amount of material in the
system
 Extensive Properties - system
does depend on the system size
or the amount of material in the
system.

IV. State and Path Functions

 – Where, F = component of force acting
ღ Path and Processes along the line of the displacement dl
 Processes: Any change that a system – SI Unit: N·m (Newton-meter) or J (Joule)
t
undergoes from one equilibrium state V
to another
dW =−PAd
A
 The path of thermodynamic states that dW =−Pd V
t

a system passes through as it goes V2

t

dW =−∫ Pd V
t
from an initial state to a final state is
known as the thermodynamic process. V 1t

* (-) Sign convention adapted for work

I No Name of the Parameter Remarks o Work (+) compression (when the

Process Held Constant
piston moves into the cylinder to
1 Constant Pressure p = constant V = (mR/P)T
(Isobaric) compress the fluid)
2 Constant Volume V = constant P = (mR/V)T o Work (-) expansion (opposite
(Isobaric) direction / the fluid make the
3 Constant T = constant pV = constant
Temperature piston to move upward)
(Isothermal)
4 Polytropic n pVn= constant An isobaric expansion
5 Adiabatic No heat flow pvY = constant
of a gas requires heat
across the
system transfer during the
boundary expansion to keep the
6 Isoenthapic h = constant h = constant pressure constant, the
work done is PdV.
 These cannot be defined for a state
(you cannot say a system has an
amount of work at a specific set of
conditions, only that it does a certain
W out =Fd=PAd=P ∆ V
amount of work to get from one state
to another, via a specified path). A path for
compression of a gas
from point 1, initial
volume V1t at pressure
P1, to point 2, volume
V2t at pressure P2. This
path relates the
pressure at any point
of the process to the
volume.
t
V2

W =−∫ Pd V
t

V 1t

o Three Modes of Work Transfer

 Boundary Work – occurs when
the volume V of a system
changes. It is used for calculating
piston displacement work in a
closed system
ღ Work
 Shaft Work - is the work done if
– performed whenever a force acts through
the system turns the shaft of a
a distance (W)
motor or compressor.
dW =Fdl
 Electrical Work – energy
transferred to the system under
 the voltage potential, voltage is
applied to a resistance in a ◊ Kinetic Energy
system that results in current - The energy of a system possesses
flow that in turn increases the because of its velocity relative to
internal energy of the system. the surroundings at rest

mu22 mu21
( )
2
mu
W= − =∆ → shows that the work
2 2 2
done on a body in accelerating it from an initial
velocity u1 to a final velocity u2 is equal to the
change in kinetic energy of the body. Conversely, if
a moving body is decelerated by the action of a
resisting force, the work done by the body is equal
to its change in kinetic energy.
a. Wb : Piston – Cylinder
b. Ws : Paddle Wheel 1 2
E K = mu
c. We : Volts I (Amps) time 2
Where,
ღ Energy m = mass in kg
 Microscopic Form – energy related to u = velocity in m/s
molecular structure called Internal
energy (U) dW =Fdl if F=ma then dW =madl
 Macroscopic Form – energy related to du dl
a= ;u=
motion or elevation of the system e.g. dt dt
KE = ½ mv2 or PE = mgz dW =m
du
dt( )dl=m
dl
dt ( )
du

 Total Energy (E): dW =mudu

1 2
E=U + KE+ PE=U + mv + mgz
2 ◊ Potential Energy
 Specific Total Energy (e): - The energy of a system possesses
E v2 because of the body force exerted
e= +u+ ke+ pe=u+ +gz on its mass by a gravitational or
m 2
 Specific Internal Energy (u): electromagnetic field with respect
U to reference surface
u=
m
W =m z 2 g−m z 1 g=m g ∆ z→ work done on a
o Energy transfers at the system body in raising it is equal to the change in the
boundary as heat and work quantity mzg. Conversely, if a body is lowered
against a resisting force equal to its weight, the
◊ Internal Energy work done by the body is equal to the change in the
The portion of the internal energy of quantity mzg.
a system is associated with the:
1. Kinetic energies of the molecules (sensible E P=mzg
energy) Where,
2. Phase of a system (latent energy) m = mass in kg
3. Atomic bonds in a molecule (chemical z = elevation in m
energy) g = gravitational acceleration in m/s 2
4. Strong bonds within the nucleus of the
atom itself (nuclear energy) ◊ Energy Conservation
5. Static energy (Stored in a system) - Law of Conservation: energy is nor
6. Dynamic energy: energy interactions at the created or destroyed, thus the
system boundary (i.e. heat and work)
 total energy of the universe is
constant.

∆ E K + ∆ E K =0
2 2
mu2 mu1
− +m z 2 g−m z1 g=0
2 2

Example 1.4
An elevator with a mass of 2500 kg rests at a level
10 m above the base of an elevator shaft. It is raised
to 100 m above the base of the shaft, where the
cable holding it breaks. The elevator falls freely to
the base of the shaft and strikes a strong spring.
The spring is designed to bring the elevator to rest
and, by means of a catch arrangement, to hold the
elevator at the position of maximum spring
compression. Assuming the entire process to be
frictionless, and taking g = 9.8 m⋅s −2 calculate:
(a) The potential energy of the elevator in its
initial position relative to its base.
(b) The work done in raising the elevator.
(c) The potential energy of the elevator in its
highest position.
(d) he velocity and kinetic energy of the
elevator just before it strikes the spring.
(e) The potential energy of the compressed
spring.
(f) The energy of the system consisting of the
elevator and spring (1) at the start of the
process, (2) when the elevator reaches its
maximum height, (3) just before the
elevator strikes the spring, (4) after the
elevator has come to rest.
Example 1.5
A team from Engineers Without Borders constructs
a system to supply water to a mountainside village
located 1800 m above sea level from a spring in the
valley below at 1500 m above sea level.
(a) When the pipe from the spring to the
village is full of water, but no water is
flowing, what is the pressure difference
between the end of the pipe at the spring
and the end of the pipe in the village?
(b) What is the change in gravitational
potential energy of a liter of water when it
is pumped from the spring to the village?
(c) What is the minimum amount of work
required to pump a liter of water from the
spring to the village?
 ღ Heat
– Flows from a higher temperature to lower
temperature
– Leads to concept of temperature as a ღ Power
driving force for the transfer of energy as – energy rate of 1 J per second
HEAT – Unit: Watt (W) = J/s
– Units:
o Calorie (cal) – quantity of heat V. Zeroth Law of Thermodynamics
which when transferred to one  When two bodies have equality of
gram water raised its temperature temperature with a 3rd body, then they
to 1oC have equality of temperature with each
o British Thermal Unit (BTU) – other
quantity of heat which when
transferred to one pound mass If T A=T C and
raised its T B=T C
o temperature to 1oF Then, T A=T B
o SI – Joule (N.m), J – mechanical
work when a force of 1N acts
through a distance of 1-meter Two bodies reaching
– Conversions: thermal equilibrium
o 1 ft.lbf = 1.3558179 J after being brought
o 1 cal = 4.1840 J into contact in an
o 1 BTU = 1055.04 J isolated enclosure.

◊ In thermodynamics, that part of the

total energy flow across a system
boundary that is caused by the
temperature difference between
the system and the surroundings.
◊ Q (+) – heat is transferred TO the
system
◊ Q (-) – heat is transferred BY the
system

Q=UA ∆T
Where,
Q – rate of heat transfer
U – empirical coefficient, over-all heat
transfer coefficient
A – area for heat transfer
ΔT – change in temperature

∆ u2
∆ H+ + g ∆ z=Q+W s → This equation is the
2
mathematical expression of the first law for a
steady-state, steady-flow process between one
entrance and one exit

If ΔKE, ΔPE, Ws = 0, thus, Q= ∫ Cp ΔT =ΔH

Q=C ∆ T and Q=mc p ∆ T → equations for

calculating the heat change (Calorimetry)