notes on thermodynamics

gabriel, akb
(skimmed from thermodynamics an engineering approach - cengel & boles,

fundamentals of thermodynamics 8th edition - borgnakke, sonntag)

1. basic concepts
fluid — characterized by low resistance to flow, and tendency to assume the
shape of its container

pure substance — homogenous in composition

system — a certain quantity/volume of matter

boundaries — region that encloses the system

surroundings — the region not within the boundary

closed system — no exchange of matter, mass does not exit the boundary
(energy like heat can)

open system — mass can exit the boundary

isolated system — neither mass or energy cross its boundaries

properties of a system
intensive property — independent of the mass of a system (T, P, ρ)
extensive property — depend on the size/extent of the mass of a system
(total mass, V, total momentum)

notes on thermodynamics 1
 V
specific property — extensive property per unit mass (specific volume v= m
)

density & specific gravity

m kg
density (ρ) — mass per unit volume ρ= (m 3)
V
V 1
specific volume (v) — reciprocal of density v= =
m ρ

state postulate
a system is a simple compressible system in the absence of electrical,
magnetic, gravitational, motion and surface tension effects.

the postulate requires that two specified properties of the system must be
independent to fix the state. two properties are independent if one can be
changed as the other remains constant.

processes + cycles
isothermal - T is constant
isobaric - P is constant
isometric - V is constant

zeroth law of
thermodynamics
two bodies are in thermal
equilibrium if both have the same
temperature even when not in
contact.

temperature conversion
T (K) = T (°C) + 273.15
T (R) = T (°F ) + 459.67
T (R) = 1.8 ⋅ T (K)
T (°F ) = 1.8 ⋅ T (°C) + 32

notes on thermodynamics 2
 ΔT (K) = ΔT (°C)
ΔT (R) = ΔT (°F )

pressure
— the normal force exerted by a
fluid per unit area. in solids, this
is called normal stress.

Pgage = Pabs − Patm

Pvac = Patm − Pabs

variation of pressure with depth

the pressure of a liquid at rest does not
change in the horizontal direction.
vertically, the pressure increases with
depth because more fluid rests on deeper
layers, like an "extra weight"

P1 = P2
the difference between P1 and P3 ,

where the ρ and g is constant, therefore

2
−ρg ∫
2
dz = −ρgz ∣∣1 = −ρg(z2 − z1 ) = −ρgΔz
1

💡 try:

notes on thermodynamics 3
 we can find hA by recalling that

VA MA /ρ MB /ρ
hA = = hB =
AA AA AB

MA /ρ MA g
PA = Patm + ρghA = Patm + ρg ⋅ ⇒ PA = Patm +
AA AA

MB g
PB = Patm + ρg(hB + h) ⇒ PB = Patm + ρgh +
AB

2. pure substances properties

pure substance —
homogenous, invariable
chemical composition
saturation temperature —
temperature at which
vaporization occurs at a
given pressure
saturation pressure —
pressure at which
vaporization occurs at a
given temperature

notes on thermodynamics 4
 💡 EXPERIMENT! CONCEPTUALIZE, UNDERSTAND.

Imagine a piston-
cylinder arrangement,
set up three times
with pressures
P1 , P2 , and P3 , where
P1 > P2 > P3 . Water is
being heated in the
tank, and the weight
of the piston is
negligible. The system
is in quasi-
equilibrium.

observations for the experiment

p3 reaches its saturation point faster than p2, p1, because at lower
pressure, the boiling point of water is lower. this is why at high
altitude, where the atmospheric pressure is lower, hikers find that water
heats up quicker.

quality (x)
quality x — ratio of the mass of vapor compared to the liquid. this quality
x is in the "dome" region of the T-v diagram.
for convention,
f - liquid

g - vapor

mg mg
x= =
mtotal mf + mg

the volume is the sum of the volume occupied by the vapor and liquid

V = Vf + Vg ⇒ vf mf + vg mg

recall that the specific volume vf = Vf /mf , vg = Vg /mg

notes on thermodynamics 5
 V mf mg
v= = vf + vg
mT mT mT

therefore, the specific volume of a pure substance is

v = vf (1 − x) + vg x

💡 Try to work out the algebra

of how the equation was
v = vf
mf
mT
+ vg

mg
mg
mT
= vf (
mT − mg
mT
) + vg

derived. if x= mT
, then v = vf (1 − x) + vg x

state postulate
for a pure substance, the state is defined by two independent, intensive
properties.

P roperty3 = f(P roperty1, P roperty2)

💡 try: check table B.1.2 Fundamentals of Thermodynamics, 8th Edition

at a pressure of 10MPa, a liquid-vapor mixture has the specific volume of

0.003 m^3/kg. find the quality of this mixture.

notes on thermodynamics 6
 from the table, vf = 0.001452m3 /kg, vg = 0.01803m3 /kg
(in any situation, don't substitute values immediately. work out the algebra
first before putting in the values. it sharpens your algebraic skills!)

v = vf (1 − x) + vg x ⇒ v = vf − vf x + vg x

−vf x + vg x = v − vf ⇒ x(−vf + vg ) = v − vf

v − vf 0.003 − 0.001452
x= = ≈ 0.0934 = 9.34%
−vf + vg −0.001452 + 0.01803

ideal gas behavior

RT a
P= − 2
v − b v − cbv + db2
wherein a, b, c, and d are parameters. if these parameters are 0, then we
end up with the ideal gas law.an ideal gas has a density ρ low enough that
its intermolecular distance is large.

ˉ is the universal gas

where R
ˉT
P V = nR
constant of 8.314 kJ/Kmol K
ˉ
R
ˉT = m
P V = nR T
M molecular weight M = m/n; n =
m/M; v = V /m

multiplying both sides by 1/m, we get the equation where ˉ /M

R=R

P v = RT

all three properties P, v and T are intensive. for the density ρ to be low
enough for Ideal Gas, then the Temperature must be high or the Pressure must
be low.

notes on thermodynamics 7
 💡 try: a 1m^3 rigid tank initially constains air at 1Mpa, 400K and is
connected to an air line. the valve is opened and air flows to the
tank until it reaches 5 MPa, at which point the volve closes and the
final temperature is 450K. Find a) initial and final mass of air in
the tank and b) if the tank eventually cools to room temperature,
300k, what is the pressure in the tank then?

a) *air, although a mixture of different

substances can be treated as a pure substance so
long as it is the same everywhere. for Air, we use
the critical constant of nitrogen, N2, for
temperature and pressure.

For N2 , Pcrit = 3.39Mpa, Tcrit = 126.2K

We can see that T > Tcrit , therefore we can use the
ideal gas law. The gas constant of air R = 0.287
kJ/kg K

P V = mRT

P1 V
m1 = = 8.71kg
RT1
P2 V
m2 = = 38.71kg
RT2

b)

T3
P3 = P2 ( ) = 3.33 MP a
T2

3. first law of thermodynamics

3.1 work and heat
recall the definition of work — "a
force causing the movement—or
displacement—of an object"

for this system,

notes on thermodynamics 8
 2
W =∫ F ⋅ dx
1

the dot product of two vectors is a scalar, therefore work is a scalar

quantity

only consider the force in the direction of the motion, therefore

disregarding parallel forces acting on the body. (in the above example,
gravitational force is acting parallel, therefore it is disregarded.)

onto a piston-cylinder arrangement,

the displacement is denoted by z . remember

that pressure is equal to the force directed
on a certain area P = F /A.
the infinitesimal displacement can be donated
by dz , as well as the infinitesimal force dF ,
where:

F = P Ak^

dz = dzk^

where k^ is a unit vector of one denoting the

direction of the piston. k^ ⋅ k^ = 1

2 2
W12 = ∫ F ⋅ dz = ∫ P Adz
1 1

where Adz is just the displacement of A, therefore:

2
W12 = ∫ P dV
1

if the system is isobaric, then P is a constant. we can reduce the integral

to

W12 = P (V2 − V1 )

2 2

notes on thermodynamics 9
 💡
2 2
W12 = ∫ P dV = P ∫
2
work out the integration by dV = P ⋅ V ∣∣1
1 1
yourself!
W12 = P (V2 − V1 ) = P ΔV

W12 and Q12 are path dependent, and not point

functions.

— work and heat are path dependent. the

displacement path affects the amount of work
done.

2
W12 = ∫ δW =
 W2 − W1
1

2
Q12 = ∫ δQ =
 Q2 − Q1
1

δQ, δW are inexact differentials.

V12 is a point function.

2
ΔV = ∫
2
dV = V ∣∣1 = V2 − V1
1

ΔV is an exact differential.

💡 Heat and work are not thermodynamic properties. They can also cross
the system boundary.

2
W12 = ∫ P dV
1

case A: piston is not moving, V is constant

W12 = 0

notes on thermodynamics 10
 case B: piston is moving, P is constant
2
W12 = P ∫ dV = P (V2 − V1 )
1

case C: piston is moving, P is NOT constant

we must know how the pressure varies with the volume, aka how does the
pressure change as a function of volume?

one case is the POLYTROPIC PROCESS, wherein P V n = constant

constant
P V n = constant ⇒ P =
Vn
plugging this into the Work equation

2 2
const. dV
W12 = ∫ n
dV = constant ∫ n
1 V 1 V

if n = 1, then const. = P1 V1 = P2 V2 if n =
 1, const. = P1 V1 = P2 V2
n n

V2 V −n ∣2 const. 1−n
W12 = const. ln ∣∣ ∣∣ W12 = const. ∣ ⇒ (V −
V1 −n + 1 1 1−n 2

plugging in the constant into the plugging in the constant into the
2 2 dV
work equation, W12 = constant ∫1 dV
Vn
work equation, W12 = constant ∫1 Vn

V2 V2 P2 V2 − P1 V1
W12 = P1 V1 ln = P2 V2 ln W12 =
V1 V1 1−n

💡 try: half a kilogram of ammonia (NH3) is contained in a piston-

cylinder arrangement. initially, it is contained at -20 degrees C
and is at 25% quality. it is then heated to a temperature 20 degrees
C, and its volume is 141% bigger than the initial volume. find the
work done in this process. (weight of piston is negligible, other
energies can be neglected)

looking at the AMMONIA Tables, we can see

notes on thermodynamics 11
 that

@T = −20∘ C, P = 190.2kP a, vf = 0.001504, vf g = 0.62184

@T = 20∘ C, vg = 0.14922, P2 = 600kP a

plugging the numbers into the equation

v1 = vf + xvf g

v1 = 0.157m3 /kg

if V2 = 1.41V1 , then

v2 = 1.41v1 = 0.221m3 /kg

@T = 20∘ C, vg = 0.14922 — the largest possible value can have and STILL be
saturated. Because v2 > vg , then the ammonia is a superheated vapor.

because P is a straight line, we can assume that the pressure can be the
midpoint between 1 and 2.

W12 = 1/2(P1 − P2 ) + (v2 − v1 )m

W12 = −204.868 kJ

💡 try: A TANK A is connected to a

CYLINDER B through an air valve.
Tank A contains 400L of Argon at
250 kPa, 30 degrees C. Initially,
Cylinder B is empty and V=0, and
it requires 150kPa pressure to
lift the piston up. The valve is
opened and Argon flows from A to
B until it is 150kPa and 30
degrees C everywhere. Determine
the work done by the argon.
ANSWER: W=40kJ

3.2 heat transfer

notes on thermodynamics 12
 sign conventions
W12 is positive when done by the
system

Q12 is positive when received by

the system

rates
Ẇ = power = work/unit time = Watts
Q̇ = heat transfer done per unit
time = Watts

1. conduction heat transfer

from molecular / electron activity

2. convective heat transfer

from bulk fluid motion

3. radiation heat transfer

from electromagnetic waves

💡 try: A saturated mixture of water at 25% quality, 0.1kg is in a

piston-cylinder tank initially at 100 kPa. In order to lift the
piston, 500 kPa pressure is required. This mixture is heated until
the temperature reaches 300 degrees C. Find the final pressure, the
work done by the water and plot (P, v).

W12 = W1a + Wa2

There is no volume change from 1-a,

so W1a is zero. For Wa2 the
pressure is constant.

W12 = Wa2 = P2 (V2 − V1 ) = P2 (m)(v2 − v

We can find v1 using the formula

v1 = vf + xvf g .

notes on thermodynamics 13
 v1 = 0.424m3 /kg

Finding v2 from the superheated

table v2 = 0.523m3 /kg

W12 = 4.91kJ

3.3 conservation of energy

A system whose initial and final states are the same is a cycle.

Win = Qout ⇒ ∮ δW = ∮ δQ

2
Because ∫1 (δQ − δW ) is path independent, this must be a property of the
system. That property is the ENERGY (E) of the system.

2
∫ (δQ − δW ) = ΔE − E2 − E1
1

or

δQ − δW = dE ⇒ Q12 − W12 = ΔE

Energy (E) is the sum of all energies of the system, aka the total energy.
This is an extensive property.

E = U + ke + pe

where U = internal energy, ke= kinetic, pe= potential

U is an extensive property, while u is intensive. U = uf mf + ug mg

💡 0.5kg water is contained inside

volume of 0.1m^3 and a pressure
it reaches a temperature of 300
and frictionless. Find the work
1-2.
a piston-cylinder, initially at a
of 0.4MPa. The water is heated until
degrees C. The piston is weightless
and heat transfer done from process

notes on thermodynamics 14
 v1 = V1
m1
= 0.2m3 /kg
@ 0.4MPa, vg < v1 < vf , so it is a
mixture.
At state 2, we can conclude that it
is superheated because T2 >
Tsat @ .4MP a
from table, v2 = 0.655m3 /kg

W12 = P m(v2 − v1 ) = 91 kJ
Q12 = U2 − U1 + W12
ΔE = E2 − E1 = Q12 − W12
Q12 = m(u2 − u1 ) + W12 = 772.27 kJ
neglecting all energies apart from
internal energy,

from table u2 = 2805kJ /kg. u1 =

uf + xuf g = 1442.5kJ /kg

notes on thermodynamics 15