THERMODYNAMICS

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

WORKING SUBSTANCE – a fluid in which energy can be stored and from which energy can be removed

FLUID – a liquid, gas or vapor, that offers little resistance to deformation

SYSTEM – that portion of the universe, an atom, a galaxy, a certain volume of space that one wishes to study

THERMODYNAMICS SYSTEMS:
1. CLOSED SYSTEM – one in which there is no exchange of matter with the surroundings; mass does not
cross its boundaries
2. OPEN SYSTEM – one in which there is a flow of mass across its boundaries
3. ISOLATED SYSTEM – one that is completely impervious to its surroundings; neither mass nor energy
cross its boundaries

PHASES OF A SUBSTANCE:
1. SOLID PHASE
2. LIQUID PHASE
3. GAS or VAPOR PHASE

PROCESSES OF PHASE CHANGES:

1. MELTING or FUSION
2. FREEZING or SOLIDIFYING
3. VAPORIZATION or EVAPORATION
4. CONDENSATION or LIQUEFACTION
5. SUBLIMATION

CLASSIFICATION OF THERMODYNAMICS PROPERTIES:

1. INTENSIVE PROPERTY – independent of the mass
2. EXTENSIVE PROPERTY – dependent of the mass and are of total values
3. SPECIFIC PROPERTY – for a unit mass and are intensive by definition

SYSTEM OF UNITS (using Newton’s 2nd law of motion)

Newton’s 2nd law of motion,

“ the acceleration of a body is directly proportional to the force applied and inversely proportional to its mass “
1 F
a∝ a∝
a ∝F and m thus, m
hence,

a=K ( mF )
or,
ma
F=
K
and,
ma
K=
F
where,
K – proportionality constant

TWO MOST COMMON SYSTEM OF UNITS

1. ENGLISH SYSTEM
- FPS (ft – lb – sec)
2. METRIC SYSTEM
- CGS (cm – gm – sec)
- MKS ( m – kg – sec)

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SYSTEM OF UNITS WHERE K IS UNITY BUT NOT DIMENSIONLESS:
1. CGS: 1 dyne force accelerates 1 gm mass at 1 cm/s2
gmm−cm
K=1
dyne−s2
2. MKS: 1 Newton force accelerates 1 kg mass at 1 m/s2
kgm−m
K=1
N −s2
3. FPS: 1 lb force accelerates 1 slug mass at 1 ft/s2
slug−ft
K=1
lb f −s 2
SYSTEM OF UNITS WHERE K IS NOT UNITY NOR DIMENSIONLESS:
1. CGS: 1 gm force accelerates 1 gm mass at 980.66 cm/s2
gm m−cm
K=980. 66
gm f −s2
2. MKS: 1 kg force accelerates 1 kg mass at 9.8066 m/s2
kgm −m
K=9. 8066
kg f −s2
3. FPS: 1 lb force accelerates 1 lb mass at 32.174 ft/s2
lb m−ft
K=32 .174
lb f −s 2

COMMON PROPERTIES OF MATTER:

1. MASS, m
- absolute quantity of matter in a body

2. WEIGHT, W or Fg
- force of gravity on a body
W or F g =mg
3. VOLUME, V
- space occupied by matter

4. DENSITY, ρ
- mass per unit volume
m
ρ=
V
5. SPECIFIC VOLUME, ν
- volume per unit mass
V 1
ν= ν=
m or ρ
1
ρ=
also, ν

6. SPECIFIC WEIGHT, δ
- force of gravity per unit volume
W or F g
δ=
V also, δ=ρg
Note:
Specific weight is to the local gravitational acceleration (g) as density is to the standard gravitational
acceleration (go).
δ ρ
=
thus,
g go

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PROBLEMS:

1. For a ballistics study, a 1.9gm bullet is fired into soft wood. The bullet strikes the wood surface
with a velocity of 380 m/s and penetrates 0.15m. Find: a) the constant retarding force in N, b) the
time required to stop the bullet, c) the deceleration in m/s2.
2. A system has a mass of 30lb. What total force is necessary to accelerate it 15 fps 2 if: a) it is
moving on a horizontal frictionless plane, or b) it is moving vertically upward at a point where
g=31,5 fps2?
3. A cylindrical drum, 2ft in diameter and 3ft high, is filled with a fluid whose density is 40 lb/ft 3.
Determine: a) the total volume of the fluid; b) the total mass of fluid in lb, slug and kg; c) the
specific volume of the fluid; d) its specific weight if g = 31.9 fps2.
4. Two liquids of different densities ( ρ1 = 1500 kg/m3, ρ2 = 500 kg/m3 ) are poured together into a
100 L tank, filling it. If the resulting density of the mixture is 800 kg/m3, find the respective
quantities of liquid used. Find also the weight of the mixture if local g = 9.675 m/s2.

PRESSURE, P
→ the force applied per unit area

ATMOSPHERIC PRESSURE or BAROMETRIC PRESSURE, Patm

→ pressure of the surroundings

ABSOLUTE PRESSURE, Pabs

→ pressure measured relative to absolute zero

GAGE PRESSURE, Pg
→ pressure measured relative to atmospheric pressure
+ GAGE PRESSURE – above atmospheric pressure
- GAGE PRESSURE or VACUUM GAGE PRESSURE – below atmospheric pressure

GRAPHICAL REPRESENTATION:

•A
} +Pg
atm. pressure
} – Pg
•B
} Patm

abs. zero pressure

Pabs of A = Patm + Pg of A and Pabs of B = Patm – Pg of B

therefore,
Pabs = Patm ± Pg
some standard atmospheric pressures:
14.696 psi , 29.92 in.Hg , 33.934 ft H2O , 760 mmHg , 101 325 N/m2 or Pa , 1.0332 kgf / cm2

FLUID PRESSURES
Patm

zo
( P+ dP ) z

At center of gravity of the differential strip,

F due to P = FT
• CG
dW

F due to ( P + dP ) = FB
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thus,
FB = FT + dW but ; FT = PA , FB = ( P + dP )A , dW = δdV , and dV = Adz
so,
dP = δdz ; since P is inversely proportional with elevation,
then,
dP = - δdz
integrating using limits,
P
z
∫ dP=−δ ∫zo dz
Patm
P−Patm =−δ ( z−z o )
P=Patm +δ( z o −z ) → absolute value
hence,
P=δ( z o −z ) → fluid gage pressure
let,
( z o −z )=h → depth from surface
therefore,
P=δh
MANOMETERS – used to measure fluid pressure
TYPES:
1. OPEN TYPE – with one atmospheric surface in one leg and capable of measuring gage pressure
2. DIFFERENTIAL TYPE – without atmospheric surface and capable of measuring only difference of
pressure.

TEMPERATURE, T
→ the thermal state of a body considered with reference to its ability to communicate heat with other bodies.

SCALES IN TEMPERATURE
1. degree Fahrenheit, °F
2. degree Celsius or Centigrade, °C

CONVERSION BETWEEN °F & °C :

°F = 1.8(°C) + 32 and °C = (°F – 32 ) / 1.8

ABSOLUTE TEMPERATURE SCALES :

1. degree Kelvin or Kelvin, °K or K
°K or K = °C + 273

2. degree Rankine or Rankine

°R or R = °F + 460

ZEROTH LAW
“ when two bodies, isolated from other environment, are in thermal equilibrium with a third body, the two are in
thermal equilibrium with each other”

MASS CONSERVATION
Law on conservation of mass states that mass is indestructible.

Relation between mass rate, density, velocity and cross-sectional area ( perpendicular to mass flow ),
m' =ρA v̄
From the law on conservation of mass,
min= Δm+mout or
' ' '
min= Δ m + mout
For a steady flow of mass, Δm=0
min=mout or
'
min=mout
'

note:
m V
m' = V '=
t and t

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PROBLEMS:

1. A pressure that can support a column of water 60cm high supports a column of a given salt solution 50cm
high. Find the density of the salt solution.
2. A hiker is carrying a barometer that measures 101.3 kPa at the base of the mountain. The barometer reads
85 kPa at the top of the mountain. The average air density is 1.21 kg/m3. Determine the height of the
mountain.
3. Determine the pressure at points A and B if the density of mercury is 13 590 kg/m3 and that of water is
1000 kg/m3.
Figure:

4. The following information are known: ρw = 1000 kg/m3 , ρHg = 13 590 kg/m3 , g = 9.8 m/s2 , PI = 500 kPa.
Determine PII.
Figure:

5. The piston shown below is held in equilibrium by the pressure of the gas flowing through the pipe. The
piston has a mass of 21 kg ; PI = 600 kPa ; PII = 170 kPa. Determine the pressure of the gas in the pipe.
Figure:

6. A new temperature scale is desired with freezing of water at 0°X and boiling occurring at 1000°X. Derive
a conversion between °C and °X. What is the conversion in determining the absolute temperature for °X
scale?
7. Two gaseous streams containing the same fluid enter a mixing chamber and leave as a single stream. For
the first gas, the entrance conditions are: A1 = 500 cm2 , v = 730 mps , ρ1 = 1.6 kg/m3. For the second gas,
the entrance conditions are: A2 = 400 cm2 , m’ = 8.84 kg/s , ν = 0.502 m3/kg. The exit stream conditions
are: v3 = 130 mps , ν3 = 0.437 m3/kg. Determine: a) the total mass flow leaving the chamber, b) the
velocity of gas 2, c) the exit area.
8. A 10ft diameter by 15ft high vertical tank is receiving water ( ρ = 62.1 lb/ft3 ) at the rate of 300 GPM and is
discharging through a 6 in. ID line with a constant velocity of 5 fps. At a given instant, the tank is half-full.
Find the water level and the mass change in the tank 15 min. later.

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ENERGY CONCEPTS

ENERGY
→ the capacity to do work or to produce some effects

POTENTIAL ENERGY, PE
→ the energy that a body has due to its position or configuration relative to earth’s surface
PE=mgz
for a change in elevation,
Δ PE=mg Δz
KINETIC ENERGY, KE
→ the energy of the body possessed by virtue of its motion
1
KE= m v̄ 2
2
for a change in velocity,
1
Δ KE= mΔ v̄ 2
2
INTERNAL ENERGY
→ the amount of potential and kinetic energy possessed by the molecules of the body and their ultimate parts owing
to their relative position and motion
→ the sum of all energies of all the molecules in the system

let: u – specific internal energy and, U – total internal enrgy

U
u=
note: U=mu and, m
ΔU
Δu=
also, ΔU =mΔu and, m
WORK, W
→ the product of the displacement of the body and the component force in the direction of the displacement
→ the energy in transition, that is, it exists only when a force is moving through a distance
W=Fd
WORK OF A NON-FLOW SYSTEM, WNF
Consider a piston-cylinder system:

L
PV plane,

P 1

dV V
V1

V2
from piston-cylinder system,
W NF=FdL but, F=PA and, AdL=dV
hence,
W NF=∫ PdV
from PV plane, note that the area under a curve or a process represents work non-flow;

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 W NF= A under curve 1−2 =∫ PdV
FLOW ENERGY or FLOW WORK, Ef or Wf
→ the work done in pushing a fluid across a boundary, usually into or out of a system

F
P V

L SYSTEM

from: W=Fd
W f =FL but, F=PA and, AL=V
hence,
W f =PV
for a change in flow energy,
ΔW f = Δ PV

ENTHALPY
→ defined as the sum of internal energy and flow energy
let, h – specific enthalpy
H – total enthalpy
H
h=
H=mh and, m
also, from definition,
H=U + PV and, h=u+Pv
for a change of enthalpy,
ΔH
Δh=
ΔH =mΔh and, m
also,
ΔH =ΔU + Δ PV and, Δh=Δu + Δ Pv

HEAT, Q
→ energy in transit (on the move) from one body to another, solely because of a temperature difference between the
bodies or systems
note: Q is positive when added to the system
Q is negative when removed or rejected from a system
also: W is positive if done by the system
W is negative if done on the system

CONSERVATION OF ENERGY
Law on conservation of energy states that energy can neither be created nor destroyed.

from law on conservation of energy,

energy entering the system – energy leaving the system = change in stored energy within the system

or,
Ein −Eout =ΔE s
E s  0
for steady flow of energy,
so,
Ein =Eout
FIRST LAW OF THERMODYNAMICS
“When heat is added or removed from a system, an equal amount of some other form of energy appears or
disappears.”

GENERAL ENERGY EQUATION FROM FIRST LAW:

for non-flow system,

Q= ΔU +W NF

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for steady flow system,
Q= ΔPE+ Δ KE+ΔU + Δ PV +W SF
or,
Q= ΔPE+ Δ KE+ΔH +W SF
note: WSF – steady flow work
SECOND LAW OF THERMODYNAMICS
1st COROLLARY – it is impossible to construct an engine to operate between two heat reservoirs, each
having a fixed and uniform temperature that will exceed the efficiency of a reversible engine operating between
same reservoirs.
2nd COROLLARY – all reversible engines have the same efficiency when working between the same two
constant-temperature heat reservoirs.

THIRD LAW OF THERMODYNAMICS

“The absolute entropy of a pure crystalline substance in complete internal equilibrium is zero at zero degree
absolute.”

PROBLEMS

1. A 400 kg mass is pulled up in a smooth inclined plane 20m long to a platform 5m above the ground.
Compute the force parallel to the plane and the work done.
2. It is required to lift five people on an elevator to a distance of 100m. The work is found to be 341.2 kJ and
the gravitational acceleration is 9.75 m/s2. Determine the average mass per person.
3. A 6L of a gas at a pressure of 100 kPa are compressed reversibly according to PV2 = C until the volume
becomes 2L. Find the final pressure and the work non-flow.
4. During reversible process executed by a non-flow system, the pressure increases from 345 kPa to 1380 kPa
in accordance with PV = C and the internal energy increases by 32.6 kJ. The initial volume is 0.085 m3.
Find the heat.
5. A reciprocating compressor draws in 500cfm of air whose density is 0.079 lb/ft3 and discharges it with a
density of 0.304 lb/ft3. At the suction, P1 = 15 psia; at discharge, P2 = 80 psia. The increase in the specific
internal energy is 33.8 BTU/lb and that the heat transferred from the air by cooling is 13 BTU/lb.
Determine the work on the air in BTU/min and in Hp.
6. A thermodynamic steady flow system receives 4.56 kg/min of a fluid whose P1 = 138 kPaa, ν1 = 0.04
m3/kg, v1 = 122 m/s and u1 = 17 kJ/kg. The fluid leaves the system at a boundary whose P2 = 552 kPaa, ν =
0.2 m3/kg, v2 = 180 m/s, and u2 = 53 kJ/kg. During passage through the system, the fluid receives 3000 J/s
of heat. Determine the work in kJ/min and in kW.

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IDEAL GAS
→ a gas in which there is no attraction between the molecules and conforms to the simple perfect gas laws

IDEAL GAS LAWS:

BOYLE’S LAW
“The volume of the gas varies inversely with the absolute pressure during the change of state provided the
temperature is constant.”
1
V∝
@ T =C , P , hence, PV =C
CHARLES’ LAW
a) “The volume of the gas is directly proportional to its absolute temperature provided the
pressure is constant.”
V
=C
@ P=C , V ∝T , hence, T
b) “The absolute pressure of the gas is directly proportional to its absolute temperature provided
the volume is constant.”
P
=C
@ V =C , P∝T , hence, T

CHARACTERISTIC EQUATION OF IDEAL GAS

PV P1 V 1 P2 V 2
=C =
T or
T1 T2
IDEAL GAS EQUATION
for gases, mR=C , where, R – gas constant
PV
=mR
then, T thus, PV =mRT
note: P and T should always be absolute
for values of R, refer to item B1, Thermodynamics by Faires
also,
R̄
R=
MW where, R̄→ universal gas constant
kJ ft−lb f
R̄=8. 3143 R̄=1545
kg−K and
lb m−R
and, MW – molecular wt. ( in kg/kgmol or lb/lbmol )

FOR COMPOUND GASES

1
MW =
y
MW =∑ x i MW i ∑ MWi
or, i
where,
xi – volume fraction of each gas constituent ( from volumetric or molal analysis )
yi – mass fraction of each gas constituent ( from gravimetric or mass or weight analysis )
MWi – molecular wt. of each gas constituent

Relation between xi and yi ,

yi
MW i
xi MW i x i=
yi
y i= ∑ MW
∑ x i MW i and i

9
also,
PV =m ( MWR̄ ) T but,
m
MW
=n→
number of moles
hence, PV =n̄ RT

SPECIFIC HEAT, c
→ the amount of heat required to change the temperature of a unit mass through one degree
heat (in energy units )
c=
mass x change in temperature
in differential quantities,
dQ
c=
mdT also, dQ=mcdT
SPECIFIC HEAT AT CONSTANT PRESSURE, cp
→ the change of enthalpy per unit mass between two states in equilibrium at constant pressure per degree change of
temperature
dH ΔH dh Δh
c p= c p= c p= c p=
mdT or, mΔT also, dT and, ΔT
then,
dH=mc p dT or,
ΔH =mc p ΔT also,
dh=c p dT and
Δh=c p ΔT
SPECIFIC HEAT AT CONSTANT VOLUME, cv
→ the change of internal energy per unit mass between two states in equilibrium at constant volume per degree
change of temperature
dU ΔU du Δu
cv = cv = cv = cv=
mdT or mΔT also, dT and, ΔT
then,
dU =mc v dT or
ΔU =mc v ΔT also,
du=c v dT and,
Δu=c v ΔT
SPECIFIC HEAT RATIO, k
→ ratio between specific heat at constant pressure and specific heat at constant volume
cp
k=
cv
Relation between cp, cv, k and R:
from,
ΔH =ΔU + Δ PV
where,
ΔH =mc p ΔT and,
ΔU =mc v ΔT and, Δ PV =mR ΔT
then,
c p =c v +R
cp cp
k= cv=
also, from
cv then,
c p =kc v and, k
hence,
kR R
c p= cv=
k−1 and, k−1
ENTROPY
→ a property of matter that measures the degree of randomization or disorder at the microscopic level
let, S – total entropy
s – specific entropy

10
 S
s=
then, S=ms and, m
CHANGE OF ENTROPY,
dQ
→ the numerical changes in the quantity being determinable from the ratio T , where dQ is a small increment
of heat and T is the absolute temperature
dQ Q
dS= ΔS=
T also, T
ΔS
Δs=
also, ΔS=mΔs and, m
CHANGE OF ENTROPY OF AN IDEAL GAS FOR ANY PROCESS
dQ
dS= Q= ΔU +∫ PdV
from, T and, also, dQ=dU +PdV

then,
T2 V2
ΔS=mcv ln +mR ln
T1 V1

also, using, ΔH =ΔU + Δ PV or, dH=dU +d ( PV )

also, dH=dU + PdV + VdP
or, dH=dQ+VdP
then,
T2 P2
ΔS=mc p ln −mR ln
T1 P1

PROBLEMS
1. A compound gas has the following volumetric analysis composition: CH4 = 50%, C2H6 = 35%, CO2 =
15%. Determine: a) MW of the compound gas, b) gas constant in BTU/lb-R and in kJ/kg-K, c) the
equivalent gravimetric analysis
2. A drum 6in. in diameter and 40in. long, contained acetylene at 250 psia and 90°F. After some of the
acetylene was used, the pressure was 200 psia and the temperature was 85°F. a) What proportion of the
acetylene was used? What volume would the used acetylene occupy at 14.7 psia and 80°F?
3. For a certain 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 518 kPaa and 27°C?
4. A gas initially at 103 kPaa and 57L undergoes a process to 620 kPaa and 17L, during which the enthalpy
increases by 16 kJ. If cv = 3.1528 kJ/kg-K, determine: a) ∆U, b) cp, c) R
5. A sphere, 1.8m in diameter, contains air at 2 MPaa and 27°C. How many drums, 150mm in diameter and
600mm long, which are initially devoid of air can be filled to a pressure of 0.345 MPaa and 18°C? Assume
that the temperature of the air left in the sphere remains at 27°C.
6. The specific heat of carbon dioxide at constant pressure can be expressed as a function of temperature;
cp=1.54 – 345.1T – 1 + 4.13 x 104T – 2 , where cp is in kJ/kg-K and T is in °K. Find the change of enthalpy of
this gas when its temperature is increased from 325°K to 1100°K.
7. Three kg of air are heated from 300°K to 800°K while the pressure changes from 100 kPaa to 500 kPaa.
Determine the change of entropy. Show that the two ideal gas equations yield the same result.
8. Two kg of a gas are cooled from 500°C to 200°C at constant pressure in a heat exchanger. Determine the
change of entropy for: a) air, b) CO2, c) He

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PROCESSES OF AN IDEAL GAS

1. CONSTANT VOLUME or ISOMETRIC PROCESS (V=C)

PV plane Ts plane

Property relation, Work non-flow

T2 P2
= W NF =∫ PdV =0
T1 P1

Change of Internal energy, Change of Enthalpy,

∆ U =m c v ∆T ∆ H =mc p ∆ T

Change of Entropy, Heat transferred,

T
∆ S=m c v ln 2 Q=∆ U
T1

Steady flow work,

W SF =−∆ PE−∆ K E−∆ PV ; if ∆ PE ∧∆ KE ≈ 0, W SF =−∆ PV

For − ∫ VdP, −∫ VdP=−∆ PV

For non-flow system with Paddle Work (Wp), consider the figure;

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