Outline

• First law of thermodynamics

• Closed systems (no mass flow)

Device for in-class thought

experiments to “prove” 1st law
Rubber stops

Features:
•Quasi-equlibrium
expansion/compression

GAS •Constant volume option

•Insulated (adiabatic)

•Non-QE shaft work

•Heat addition/rejection

ICE

Experiments
• Starting from state 1, consider . . .
– Insulated (adiabatic), fix volume, do 8 kJ of
shaft work on system. Then measure change
in energy to be 8 kJ so ∴−Wsh = E2 − E1 = ∆E
– Insulated, compress gas doing 10 kJ of
boundary work. Then measure change in
energy to be 10 kJ ∴−Wb = ∆E
• Initial conclusion: For adiabatic process,
amount of work done is equal to change in
energy for closed system ∴ −W = ∆E when Q = 0

1
 More experiments
– Fix volume, no shaft work, add 10 kJ of heat.
Then measure change in energy to be 10 kJ

∴ Q = ∆E when W = 0

– Add 15 kJ of heat and do 6 kJ of shaft work.

Then measure change in energy to be 21 kJ
∴∆E = Q − W

Still more experiments

– From state 1 cause a change to state 2 by several
processes
• Compress gas doing 9 kJ of boundary work adiabatically so

∴−Wb = −( −9) = ∆E
• Do 9 kJ shaft work adiabatically so
∴−Wsh = −( −9) = ∆E
• For all adiabatic processes between two
specified states of closed system, net work is the
same regardless of the nature of the system or
details of the process

Illustration
• Energy change of
system during a
process is equal to
net work and heat
transfer between the
system and its
surroundings

2
 Summary of experimental findings
• For closed system (Joule, 1800s):

Q − W = ∆E
Net energy transfer to system Net energy increase of system
as heat and work
• Above is first law of thermodynamics
• E is property (point function)
• Q, W are path functions (except when one or the
other is zero)

Other forms of the 1st law

Q − W = ∆E = ∆U + ∆KE + ∆PE

= m(u2 − u1 ) + m (V22 − V12 ) + mg ( z2 − z1 )

1
2
Q − W = ∆U (stationary system)
q − w = ∆e (per unit mass)
δ q − δ w = de (differential form)
dE
Qɺ − Wɺ = (rate form)
dt
Q − W = 0 (cyclic process)

Example
• A rigid tank contains a hot fluid that is cooled while being
stirred by a paddle wheel. Initially, the internal energy of
the fluid is 800 kJ. During the cooling process, the fluid
loses 500 kJ of heat, and the paddle wheel does 100 kJ
of work on the fluid. Determine the final internal energy
of the fluid. Neglect the energy stored in the paddle
wheel.
Q − W = ∆E = ∆U
−500kJ + 100kJ = U 2 − U1 = U 2 − 800kJ
∴U 2 = 400kJ

3
 Outline
• Phase and pure substance
• Features of phases of matter
• Phase change processes
• Property diagrams

Phase and Pure substance

• Phase refers to quantity of matter that has same
chemical composition and physical structure throughout
e.g. all solid, all liquid, or all vapor (gas)
• A system can contain more than one phase e.g. system
of liquid water and water vapor (steam) contains two
phases
• A pure substance with fixed chemical composition
throughout i.e. water, N2, He, CO2, etc.
• A mixture of chemical elements or compounds is still a
pure substance as long as mixture is homogeneous i.e.
air
• A mixture of two or more phases is still a pure substance
as long as chemical composition of each phase is same
i.e. ice and liquid water but not liquid and gaseous air

Phases of a pure substance

• Solid – molecules are closely packed and arranged in a 3D
pattern (lattice) which is repeated throughout solid e.g. long
range order
• Due to closely packed nature attractive forces between
molecules are large and keep them at fixed positions e.g.
definite shape and size
• Molecules maintain their position but oscillate about this
equilibrium position and velocity of molecules is related to
temperature
• Higher temperature results in higher velocity and may be
high enough to overcome attractive forces and groups of
molecules may break away - melting

Temperature and molecular motions

Molecular interactions

4
 Phases (cont.)
• Liquid – chunks of molecules float about
each other but w/in each chunk molecules
maintain orderly structure e.g. short range
order
• Definite volume but fluid shape
• Slight increase in distance between
molecules over solid (except water where
solid is less dense – ice floats in your
drink)

Phases (cont.)
• Gas – molecules far apart w/ no molecular
order
• Molecules move about at random colliding
w/ each other and walls of container
• Shape and volume defined by container
• At low densities intermolecular forces are
very small and collisions are the only mode
of interaction i.e. ideal gas
• Much higher energy levels than liquid/solid

Phase change schematic

C
on
Gas Va
de
ns
at
ENTHALPY

p io
or n
iz
at
Sublimation

io
Deposition

in g Liquid
ez
Fre
g
ltin
Me
Solid

5
 Phase change processes
• Practical situations involve two phases of a pure
substance existing in equilibrium
• Water exists as mixture of liquid and vapor in
boiler and condenser of steam power plant
• Refrigerant turns from liquid to vapor in freezer
• Most important cases involve liquid and vapor
phases
• We will illustrate using water . . .

Constant pressure phase change

experiment – subcooled liquid
• What happens when we heat
water at constant pressure?
• Consider water at 1 atm, 20 C,
e.g. tap water, in a piston-cylinder
device
• It is called compressed or
subcooled liquid (CL or SL)
because it is not about to vaporize
(boil)
• Compressed suggests above
boiling P at give T
• Subcooled suggests below boiling
T at given P

Saturated liquid state

• Add heat, T rises to say 40 C, liquid
water expans slightly, specific
volume increases, piston moves up
slightly
• P still 1 atm (why?)
• Water still compressed liquid
• Add more heat until T=100C
• Still liquid but any more heat will
cause vaporization
• Liquid about to boil is called
saturated liquid (can’t “hold” any
more heat) (SL)

6
Saturate liquid-vapor mixture state
• Add more heat
• T=constant as energy goes
into vaporization process
(phase change); breaking
bonds
• Midway we have ½ liquid and
½ vapor; continue to add heat
until all liquid is vaporized
• Saturated liquid-vapor
mixture (SLVM)

Saturated vapor state

• Entire cylinder contains
vapor
• Any heat loss, no matter
how small, will cause some
vapor to condense (phase
change from vapor to liquid)
• Vapor is about to condense
• Saturated vapor (SV)

Superheated vapor state

• Single-phase (vapor)
• Add heat
• T and specific volume
increases
• At say 300 C if we transfer
some heat away T will
decrease but no
condensation
• Not about to condense
• Superheated vapor (SHV)

7
 T-v diagram of constant pressure
phase change process
SHV
SL SLVM

CL SV

Saturation temperature and

pressure
• The temperature at which water starts
boiling depends on the pressure
• If pressure is fixed, so is boiling
temperature
• For example, water boils at 100 C at 1 atm
• If P was 5 atm (add weights to piston)
boiling would occur at 151.9 C

Saturation temperature and

pressure (cont.)
• At given P, T at which pure substance
starts boiling is saturation temperature Tsat
• At given T, pressure for boiling is
saturation pressure Psat
• Example: At P=101.35 kPa, Tsat=100 C; at
T=100 C, Psat=101.35 kPa
• Tsat= f (Psat) during phase change; not
independent and cannot be used to fix
state (see Fig. 2-12)

8
 Repeat constant P phase change
experiment at different P
• Add weights to piston to
change P
• Water boils at higher T as
P increases
• Specific volume of SL is
larger
• Specific volume of SV is
smaller than at 1 atm
• Horizontal line connecting
SL and SV states shorter
• Critical point (next slide)

Critical point
• Point at which SL and SV states identical
• Above critical point there is no sharp
difference between liquid and vapor
• Tcr, Pcr, vcr = 374.14 C, 22.09 MPa,
0.003155 m3/kg
• For other substances critical point values
tabulated in A-1

Connect the dots . . .

• SL/SV states connected by SL/SV lines

• They meet at critical point forming wet dome
• T=const. phase change by decreasing piston weight;
note downward slope of T=cont. lines

9
Extension to include solid phase

• Most substances contract during solidification (freezing); except

water which expands during freezing
• Under some conditions all three SLV phases can coexist in
equilibrium
• On P-v or T-v diagrams these triple states form a triple line on a P-T
diagram at triple point

P-T diagram and triple point

P-v-T surfaces
• Recall that state of a simple compressible
substance is fixed by 2 independent,
intensive properties e.g. state postulate
• Recall equation z=z(x,y) represents a
surface in space, so we can represent P-v-
T relationship as surface in space i.e. T-v
space with P as height (see next slide)
• P-v, T-v, P-T diagrams are projections
from this 3D plot

10
 P-v-T surfaces

Contract on freezing Expand on freezing (like water)

Summary
• Is iced water a pure substance?
• What is the difference between saturated liquid and
compressed liquid?
• What is the difference saturated vapor and superheated
vapor?
• Is there any difference between the properties of
saturated vapor at a given temperature and the vapor of
a saturated liquid-vapor mixture at the same
temperature?
• Is it true that water boils at higher temperatures at higher
pressures? Explain.
• What is the difference between the critical point and the
triple point?

Outline
• Property tables
• Property evaluations

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 Property tables
• Properties are listed in the form of tables i.e.
steam tables
• SI and English unit versions
• They list property information for each region of
interest, such as SHV, CL, and SLVM regions
• Looking at steam tables you find enthalpy, h,
and entropy, s, which we have not discussed yet
• Entropy later, enthalpy now . . .
• H=U+PV (kJ) or h=u+pv (kJ/kg)
• P, T, v, u, h, and s data are tabulated

Saturated water tables

(A-2 T table, A-3 P table)

u fg = u g − u f h fg = hg − h f
s fg = s g − s f

Examples
A rigid tank contains 50 kg of saturate liquid
water at 90 C. Determine the pressure in the
tank and volume in the tank.
P = Psat @90C = 0.7014bar = 70.14kPa ( A − 4)
υ = υ f @90C = 0.001036m3 / kg ( A − 4)
V = mυ = (50kg )(0.001036m3 / kg ) = 0.0518m3

Can you confirm these numbers from the tables listed?

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 Examples
A piston-cylinder device contains 2ft3 of
saturated water vapor at 50 psia. Determine T
of vapor and mass of vapor inside cylinder.
T = Tsat @50 psia = 281.03F ( A − 3E )
υ = υ g @50 psia = 8.518 ft 3 / lbm ( A − 3E )
V 2 ft 3
m= = = 0.235lbm
υ 8.518 ft 3 / lbm

Can you confirm these numbers from the tables listed?

Saturated liquid-vapor mixture

• During vaporization substance exists as part liquid and
part vapor i.e. mixture of SL and SV
• We need to know proportions of each phase in mixture
• We define quality, x, as ratio of mass of vapor to total
mass of mixture
mvapor
x≡ mtotal = mliq + mvap = m f + mg
mtotal
• x always between 0 and 1, i.e. x=0 for SL and x=1 for SV
• x can be used as one of two independent, intensive
properties to fix state
• Properties of SL and SV are same in mixture as if alone

SLVM properties
• We normally pretend SLVM is homogeneous mixture

V = V f + Vg ⇒ mtυ av = m f υ f + mgυ g
m f = mt − mg → mtυ av = ( mt − mg )υ f + mgυ g
÷mt → υav = (1 − x )υ f + xυ g = υ f + xυ fg
∴ x = (υ av − υ f ) / υ fg
• x has no meaning outside of the wet dome
y = y f + x y fg x = ( y − y f ) / y fg
y f ≤ y ≤ yg (usually drop av subscript)

13
 Quality on the wet dome

x = 0.5

x = 0 x =1 x = (υ av − υ f ) / υ fg

υ f υ av υg

Examples
• A rigid tank with 10 kg of water at 90 C. If 8 kg
of water is in liquid form and rest is in vapor
form, determine (a) P in tank, (b) V of tank.
P = Psat @90C = 70.14kPa ( A − 2)
υ f @90C = 0.001036m3 / kg , υ g @90C = 2.361m3 / kg ( A − 2)
V = V f + Vg = m f υ f + mgυ g
= (8kg )(0.001036m3 / kg ) + 2(2.361m3 / kg ) = 4.73m3
x = mg / mt = 2 /10 = 0.2 ∴υ = υ f + xυ fg =
OR = 0.001036m3 / kg + 0.2(2.361 − 0.001036) m3 / kg
= 0.473m3 / kg ⇒ V = mυ = 10(0.473) = 4.73m3

Superheated vapor
• Table A-4
• Single phase region
to right of SV line
• T, P independent and
fix state
• P<Psat at given T
• T>Tsat at given P
• v, u, h > SV values at
given P or T

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 Example
• Find internal energy of water at 20 psia
and 400 F
Tsat @ 20 psia = 227.96 F ( A − 3E );
T > Tsat ∴ SHV ; u = 1145.1Btu / lbm( A − 4 E )

• Find temperature of water at P=0.5 MPa

and h=2890 kJ/kg
hg @0.5 MPa = 2748.7kJ / kg ; h > hg ∴ SHV ⇒ T = 216.4C
T , C h, kJ / kg
200 2855.4
250 2960.7

Linear interpolation
• Assumes any two data points connected by straight line
(set slopes equal to find missing value)
A B
100 5

130 X
200 10

130 − 100 x − 5
=
200 − 100 10 − 5

Compressed liquid
• Not much data due to relative independence of CL
properties with pressure
• They are incompressible i.e. change in pressure barely
changes v, T, u, etc.
• A good approximation if data is unavailable is to treat CL
as SL at same T (properties of CL due vary with T)

y ≅ y f @T h ≅ h f @T + v f ( P − Psat )
• P>Psat at given T (CL) and T<Tsat at given P (SC)
• v, u, h < SL values at given P or T

15
 Example
• Determine internal energy of CL water at
80 C and 5 MPa using (a) data from CL
table and (b) SL data. Error?
Psat @80C = 47.4kPa; P = 5MPa > Psat
∴ CL ⇒ u = 333.72kJ / kg
vs. u ≈ u f @80C = 334.86kJ / kg (0.34%)

Reference state and values

• u,h,s cannot be measured directly
• P,T,v can be measured directly
• Changes in u, h, s computed using derived relations with
P, T, v
• Note: only changes can be computed not u, h, s, at
specific state
• But fortunately in 1st and 2nd law’s only changes in these
properties is needed
• We choose a convenient reference state and ste
properties to zero at that state
• For water, u=0, s=0, at 0.01C for SL state; h=u+pv; could
have negative values relative to reference; different ref.
state for different substances; ref. state cancels out
(u 2 − uref ) − ( u1 − uref ) = u2 − u1 = ∆u

Summary
• What does the saturated water table represent?
• What is quality? Does it have any meaning in
SHV region?
• What if h data is needed at T=125 C and the
table only lists h data at T=100 and T=150 C?
• In the absence of CL tables, how is specific
volume of CL at given P and T determined?
• Does reference point selected for properties of a
substance have any effect on thermodynamic
analysis? Why?

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