12

Consider the following (old) scheme to produce fresh water from sea water. As a first
approximation, let’s assume that the properties of sea water are similar to those of pure water.
Assuming !̇ 1 = 1 kg/s (about 1 L/s), determine:

(a) The mass flow of fresh water produced, !̇ 8

(b) The rate of heat transferred to the sea water at the heater, #̇
(c) The power required by the pump, $%̇
(d) How much heat per second is transferred to the sea water at the heat exchanger?

miemzems mu Ms inzeing
Fresh water
inge FLASHSEPARATOR

Mielkgy
0 7
O
IF
15 [ C]
P isCONSTANT IN HEATEXCHANGERS Brine
Sea water
HEATERSANDFLASHSEPARATORS
PzIÉPy 8586
All the thermo properties of water needed to solve this problem are summarized in the following
tables:
Pt
Pz
● Water – saturation properties LOOKS
LV
P (kPa) T (°C) (
vˆ m 3 kg ) ĥ (kJ kg )

00
Sat. Liq. Sat. Vap. Sat. Liq. Sat. Vap.

00
100 99.606 0.0010432 1.6939 417.50 2674.9

In
● Water – subcooled liquid

P (kPa) T (°C) (
vˆ m 3 kg ) ĥ (kJ kg )
100 15 0.0010009 63.076

88O
100 35 0.0010060 146.72
700 15 0.0010006 63.650

O
700 150 0.0010904
O
632.32

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VIEW PHOTOS

‘Most powerful crossovers and SUVs on sale today’

https://www.caranddriver.com/features/g26339934/most-powerful-suvs/
 2

Estimating values of thermodynamic properties: for a pure substance, given

I
values of two independent intensive properties, how to determine the values of
other thermodynamic properties

The ‘old fashioned way’: steam tables (water), tables for other substances
Appendix B of Koretsky
Also in Perry’s Chemical Engineering handbook, other books

Different software, e.g., Thermo Solver software (with Koretsky’s textbook)

Chemical Engineering App Suite HD for iPhone and iPad: Prof. Jason Bara,
Chemical & Biological Engineering, University of Alabama:
http://itunes.apple.com/us/app/chemical-engineering-
appsuite/id526158171?mt=8

NIST website: http://webbook.nist.gov/chemistry/fluid

Interpolation with the steam tables (LearnChemE, Chemical and Biological

Engineering, University of Colorado Boulder)

Another example of linear interpolation, this time to estimate saturation

pressure: http://www.youtube.com/watch?v=4Y0vNuOUbbw

An example of a ‘double’ interpolation:

http://www.youtube.com/watch?v=b1DeF2q2ZnU

EXAMPLE Find Li TE Zoo c USING DATABelow

Iyypah
C
F Zoo

Y Y xD
II JA
Te 203 C
Pa 103kt
Te 205 C
 3

I
PvT behavior, pure substances:
T-v diagram
PECONSTANT

LITER
IBAN Afton

LVMixture
http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/pvtexp.html#c1

to

I
ABOUT

Figure adapted from Koretsky

to
SYSTEMS
For L
xemgmEE.IT
Waconstant

wit I'm
here it
exerted
http://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter2a.html
 4

U ⎡ kJ ⎤ U ⎡ kJ ⎤
u= ; û =
n ⎢⎣ kmol ⎥⎦ m ⎢⎣ kg ⎥⎦
Internal energy

û = x ûv + (1− x ) ûl

h=
H ⎡ kJ ⎤
E ; ĥ =
H ⎡ kJ ⎤
Enthalpy iv airhi
n ⎢⎣ kmol ⎥⎦ m ⎢⎣ kg ⎥⎦
ĥ = x ĥv + (1− x ) ĥl ie liehe
App. B textbook: Δĥlv = ĥv − ĥl
Δûlv = ûv − ûl
 5

Second Law of Thermo

in
To understand this law, we will follow its historical development and thus start
by studying heat engines: MACHINES
OPENATINACE
PRODUCE POWER FROMHEAT

BEINGBURNED
HotTSOURIGFUEL
STEAM
f

I Ip H2O

SEIP RANKINE
Katinka
LearnChemE: http://www.youtube.com/watch?v=BA77fu3zAbs

Ét
Thermal efficiency:

Inkling

It
t an
E
 6

Can reverse energy flows in heat engine, obtain machine that consumes work to
take heat out of a low-temperature reservoir and send it to a hot-temperature
reservoir (a refrigerator):

en

Food Adapted from Levenspiel’s book

.
QH

IIe R134a EYE . R-134a

W

L Mix Ann
lout
.
compressionc
rapor
coup Adapted from SVNA’s book, 7th ed.
Qc
LearnChemE: https://www.youtube.com/watch?v=TBEEt8x4nSo

Coefficient of performance (refrigerator efficiency):

ioitwl
qq.gg I
hit lien lied
idFyggi
É BSO 1
CAN BE
 7

Example: From an engineering point of view, it has been proposed that Hell
must be a completely isothermal (and flat) place. Explain this argument from
the thermo point of view.
IF THEREIS A DTINHELL
AN ENGINEER COIDDEVICE A
FATENINE ProducePOWER
1 4 80 AND POWERAN A C UNIT
KEEP THEIR HOUSECOOL

FELL
A HEATENGINE
REFRIGERATOR
IS ISOTHERMAL AT O
USING A AT TH
Tc
TO PRODUCE W POWER
Second Law: Clausius postulate

to
l pay
I
Heat cannot spontaneously flow ‘uphill’; the ‘perfect’ refrigerator/heat pump
does not exist.

Second Law: Kelvin-Planck postulate HEAT ENGINES

iii
Olya
Heat engines cannot convert 100% of heat into work
 8

If a thermal efficiency of 100% is not possible for heat engines, what is the
upper limit for this efficiency? EVERSIBLE inn
fwmgyAUPMCESSESA.AE
Carnot theorems (1824):
1. Reversible heat engines have the highest efficiency between any two
temperatures TH and TC
2. All reversible heat engines operating between the same two
temperatures TH and TC must have the same efficiency
3. For the same high temperature TH, the engine that operates between
reservoirs with the larger ΔT has the higher efficiency
Proof: any thermo book (see, e.g., Koretsky.)

Based on the 2nd Theorem of Carnot, we can analyze the simplest reversible heat engine, and try to derive

t
an expression for its efficiency. The simplest reversible heat engine is based on the Carnot cycle:

(See ‘Derivation of efficiency of a Carnot cycle’ for proof of this equation)

IDEALGAS
 9

For a refrigerator:

QC 1
b = coefficient of performance Þ b = = FEntidenaton
W QH
-1
QC
a
For a refrigerator based on the Carnot cycle:

EIII
Entropy

HEIKE
For a Carnot cycle:

7
SYSTEM's
41114 FEE
EGAS
unsent
one É D

O
Ecco Ting
Screencast: https://www.youtube.com/watch?v=m6XaSGQi2wA
 10

What about an arbitrary reversible cycle? Any reversible process can be

represented using a combination of 2 adiabatic and 1 isothermal trajectories
(See notes for proof)

Therefore, any ‘arbitrary’ reversible cycle can be represented using an infinite

number of small Carnot cycles:

FOR EACHTINYCARNOTCYCLE
0
SEE SEE
ADDING OVERALLCANNOTCYCLES

FEEEII.EE
INFINITESIMAL
CANNOTCYCLES OVERCycle

The previous equation suggests that the quantity δQ/T exhibits the
characteristics of a thermodynamic property (such as T, P, V, U, H).
I
o
goat

PEG
Let’s define:
dr O

dis
E entropy
E
 awe l
11

Now, what is entropy? What is its physical meaning (if any)?

ÉÉ
Third law:
From Statistical Thermo: S = kB lnW For a perfect crystal at 0 K, S = 0

Boltzmann constant

Solid ice Liquid water Gaseous steam

(0 °C, 1 bar) (25 °C, 1 bar) (150 °C, 1 bar)
Figures taken from J. W. Tester and M. Modell, “Thermodynamics and its applications” 3rd ed. (1997)

Ssolid < Sliquid < Svapor Entropy is a measure of ‘molecular disorder’

dQrev
= dS Entropy [kJ/K] Similarly:
T
U ⎡ kJ ⎤ U ⎡ kJ ⎤
u= ; û =
s=
S é kJ ù
; sˆ =
S é kJ ù n ⎢⎣ kmol ⎥⎦ m ⎢⎣ kg ⎥⎦
n êë kmol K úû m êë kg K úû H ⎡ kJ ⎤ H ⎡ kJ ⎤
h= ; ĥ =
X n ⎢⎣ kmol ⎥⎦ m ⎢⎣ kg ⎥⎦
sˆ = x sˆv + (1 - x ) sˆl MI
G û = x ûv + (1− x ) ûl
ĥ = x ĥv + (1− x ) ĥl

Et
App. B textbook: Dsˆlv = sˆv - sˆl
Dhˆlv = hˆv - hˆl
Duˆlv = uˆv - uˆl
t
Entropy for ideal gases → see notes

si si girl E
si
sitting rent
 12

2nd Law for closed systems

n
Entropy was defined based on a reversible cycle. However, real cycles (and

Si
processes) are not reversible, due to the presence of irreversibilities (e.g.,
mixing of components, heat transfer due to temperature differences, etc.)

For irreversible (real) processes:

É
i

Y
O ed I ILATED
System
NOENERGY OR
ΔSuniv = ΔSsyst + ΔSsurr ≥0 MASSLEAVESUNIVERSE
1 = initial state
δ Qsurr
∴ ( S2 − S1 )syst + ∫
2 = final state
≥0
Tsurr
Qsunn dsyst ARE
Q
∴ ( S2 − S1 )syst + surr ≥ 0 TORRECONSTANT SURROUNDINGS
Tsurr LARGERTHAN
See notes for proof (2nd SYSTEM
Qsyst law for closed systems)
∴ ( S2 − S1 )syst − ≥0
Tsurr
 13

A piston-cylinder system contains 100 L of air at 400 kPa and

25 °C. 15 kJ of heat are transferred from a hot source at 100
°C, and the air expands isobarically. Determine:
(a) The final temperature of air
(b) The entropy generated during the process. Is this process
possible? What if the hot source is at 0 °C?
Q
Assume air is an ideal gas with constant Cp, Cv

Cˆ p = 1.005 kJ (kg K ) ; Cˆ v = 0.718 kJ (kg K ) ; Rˆ = R M = 0.287 kJ (kg K ) 100 °C

M = 28.97 kg kmol
14
 15

2nd Law for open systems (steady-state)

dSuniv dSsyst dSsurr

= + ≥0
dt dt dt
dSuniv ⎡ Q! surr ⎤
∴ = 0 + ⎢ ∑ ( m! in ŝin )surr + − ∑ ( m! out ŝout )surr ⎥ ≥ 0
dt ⎣ Tsurr ⎦
dSuniv ⎡ Q! syst ⎤
∴ = 0 + ⎢ ∑ ( mout ŝout )syst −
! − ∑ ( min ŝin )syst ⎥ ≥ 0
!
dt ⎢⎣ T surr ⎥⎦

See notes for proof (2nd law for open systems)

Example:
From Levenspiel’s book

• Assume air is an ideal

gas, Cp = 29.1 J/(mol K)
• Device has no energy
input, no moving parts,
and loses no heat to the
surroundings

LearnChemE: http://www.youtube.com/watch?v=o4qwEgj9k1A
16
 17

Isentropic efficiencies of turbines, compressors, pumps

ηturbine =
W!real
=
(
m! ĥ2 − ĥ1 − Q! )
W!is (
m! ĥ2,is − ĥ1 ) 1 = in
2 = out

ηcompressor =
W!is
=
(
m! ĥ2,is − ĥ1 )
W!real ( )
m! ĥ2 − ĥ1 − Q!

W!is m! ( ĥ − ĥ )
2,is m! v̂ ( P − P )
1 1 2 1
η pump = = =
W! real m! ( ĥ − ĥ ) − Q!
2 1
m! ( ĥ − ĥ ) − Q!
2 1

(See notes for proof)

18
19