1

CHME 5101: FUNDAMENTALS OF CHEMICAL ENGINEERING ANALYSIS

PART 2: THERMODYNAMICS

Primary textbook reference: Milo D. Koretsky, Engineering and Chemical

Thermodynamics 2nd ed., Wiley, 2013

Thermodynamics original definition: how to convert heat into ‘useful work’,

e.g., motion (from the ‘Industrial Revolution’, late 1700s)

Thermo based in four laws:

Zeroth Law (R. H. Fowler, 1931):

TA
Two bodies A and B are in thermal equilibrium
A B C (have same T); and if bodies B and C are also in
thermal equilibrium ® TBI
Tate
Basis of temperature measurements:
• B = thermometer TACTB
• Put A in contact with thermometer until thermal equilibrium is achieved
• Put C in contact with thermometer
• If no changes observed in thermometer ® TBIETBTC
First Law (~ 1844) CONSERVATION OF
ENERGY

FEI
Block A Block B Time
20 °C 40 °C

Insulated cooler
 2

Second Law ( ~1824): can be stated in many different ways

FLOW UPHILL

TRANSFORMED INTO WORK

A SYSTEM SPONTANEOUSLY
MOVETOWARD A MORE
DISORDERED STATE

Nz Oz
Taken from Levenspiel’s book

Third Law (~1906)

“The entropy of a pure substance that exists as a perfect crystal at T = 0 K is

equal to zero”

Establishes an absolute reference point to measure entropy (important for

Statistical/Molecular Thermodynamics)
 Pkn3 Rt
Edvicibrim IEEE
Thermodynamics important for Chemical Engineering: OFSTATE
EOTATION
Given values for some properties (e.g., temperature, density), models can be
developed and used to predict values for other properties (e.g., pressure,
specific heat, etc.)

Predict phase changes and chemical reactions in systems: phase equilibrium and
chemical equilibrium (pure substances, mixtures)

Concept of equilibrium = upper limit / best case scenario for chemical processes:

ELECTRICITY
• Maximum (equilibrium) conversion of heat into useful work
n

a
N
IEEE MAXIMUMPRODUCTION OF
POWER

F FromHEAT

• Maximum (equilibrium) separation of components in a mixture

I Ininentanov Yi
I METE richer in WATERS Xi
• Equilibrium chemical reactivity in a mixture

THERMO DETERMINES
At B E C MAXIMUMAMOUNT OF C
T P
• In equilibrium, time is usually unimportant
tea
• Real chemical equipment limited by kinetics, transport efficiency
• Flow rates
• How fast heat is transferred

I
• How long will it take to separate two components from a mixture
 4

• Time/reactor volume to react a significant amount of A + B into C

• Relation between thermo and kinetics (LearnChemE):
LEARNCHENEY http://www.youtube.com/watch?v=uJXOCpDhuSQ
t

FIRST LAW OF THERMO ENERGY BALANCES

‘Energy’ can’t just appear from nowhere. If a system gains ‘energy’, it must have
come from outside of it.

se
Ine
Energy cannot be created or destroyed. Energy can only change from one form
to another, or can be added to the system from the surroundings

• 1 J = 1 N.m = the energy needed to lift a cube of butter 1 m into the air

• 1 cal = 4.184 J = the energy needed to heat 1 g of water in 1 °C

• 1 BTU = 1055.056 J = the energy needed to heat 1 lb of water in 1 °F

IF
• 1 kW.hr = 3.6 x 106 J = a measure of electrical work (costs about 21 ¢ in MA)

• Power = energy / time

IT First Law of Thermo, closed systems NOMASS ENTERING LEAVING SYSTEM

Ways to change the energy of a closed system:

1. Changing the potential energy of an object, ΔEp: change its location in a

force field (gravitational, electrical, magnetic)

2. Changing the kinetic energy of an object, ΔEk: change its velocity

It
ENERGY STOREDinMOLECULES
Is
3. Changing the internal energy of an object, ΔU: can be done in various
ways:
• Change its temperature (heat or cool)
 5

• Change its phase (solid to liquid, liquid to gas, etc.)

F
• Change its molecular arrangement (chemical reaction):
C3H8 + O2 ® CO2 + H2O + heat

• Change atomic structure (nuclear fission); or breakup large atoms into

small fragment atoms (e.g., uranium fission)

• Combine little atoms into large atoms (nuclear fusion)

4. Heat: add or remove energy from a system, by contact with a hotter or

cooler body

WII Isi
5. Work: all ways of changing the energy of a system other than by adding or
removing heat:
• Push-pull work we ff.de
FEEDS E lot
Agro
• pV work

• Electric, magnetic work

If wefedr
GASSPENDSENERGY

2
PUSHINGPiston out
• Elastic work (winding up a spring)

Expressions for the 1st Law of Thermo, closed systems

QIEDEK TERM
twind
For GASES unis Tye Tye I go
For typical systems in Thermo (gases, liquids): kinetic and potential energy
terms are usually negligible compared to internal energy, thus

father
 6

Enthalpy, specific heats: hfkJkmd

e
æ dq ö
CV = ç ÷
æ dq ö
CP = ç ÷ niftily
è ¶T øV è ¶T øP
O O riffing
æ ¶u ö æ ¶h ö
\ CV = ç ÷ (see notes for proof \ CP = ç ÷
è ¶T øV of these equations) è ¶T ø P
Where h = u + Pv = enthalpy P KPa
Units:
E
FEET IEEE
Screencast “What is enthalpy” (LearnChemE):
TICK
http://www.youtube.com/watch?v=AK9JIFyzqMY
I
Internal energy, enthalpy, specific heats for ideal gases
a
MOLECULES DONOTINTERACTWITH
Joule experiment
EACH OTHER

p p
Gas Vacuum Gas
HIGHT
Gas

• Two interconnected flasks, immersed in water

• Gas initially at P1, T1 (same T as the water bath)
• Valve is opened, and system is left alone for a long time
• Gas reaches mechanical equilibrium (pressure in both flasks is equal); gas
also reaches thermal equilibrium (temperature of gas in both flasks becomes
equal)
• For an ideal gas (a gas at low pressures), Joule found that T2 = T1
• From the Joule experiment, we can conclude that:

h hH TEEN
LIFE
See additional notes for proof
due Crigdt MAYERRecation

Gig Crier
dhe gigg
 7

i
I
ME CONSTANT
a CLOSED SYSTEM

P 75hPa RT Rena
PV MET 3.136 1079
I I L
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Pee 150mg
Tz T E 1000K
h MET
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I
Pz Pz 150kPa
43 Bff
2504
o.o is m3
V3
Y
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b Wi z Fdr
compression
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VITRELATE IDEALGAS
P NT
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T
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31.31 G REMOVING HEAT FROM SYSTEM
 9

A graph illustrating the range of validity of the ideal gas model (for water)

IsoBans
Pc P CONSTANT
A VALID FORGAS
n

coup
ANDOR HIGHT

HIT pack

p
vvgf.jo
http://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter2b.html

First law of thermo for open systems MASSENTERS LEAVES SYSTEM

a
General expressions IN OUT GENERATED ACCUMULATED

dm V! vel ⋅ A
Mass balance: å m! in - å m! out =
in out dt
m! =
v̂
=
v̂
= ρ ⋅ vel ⋅ A

nitpa
Energy balance:
in
æ
è
vel 2
2
ö
ø out
æ
è
she vel 2
2
ö dE
Q! + W! + å m! in çç hˆin + in + gzin ÷÷ - å m! out çç hˆout + out + gz out ÷÷ =
ø dt

E afewQ! + W! + ⎛ velin2 ⎞ ⎛ 2
velout ⎞ dE
∑ m! in ⎜⎝ ûin + Pin v̂in + 2 + gzin ⎟⎠ − ∑ m! out ⎜⎝ ûout + Pout v̂out + 2 + gzout ⎟⎠ = dt
in out

(see additional notes for derivation of these equations)

F
Screencast on flow work (LearnChemE):
http://www.youtube.com/watch?v=bspnf00z4CU
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Steady-state:
(1) Rate of heat transfer, power, mass flows are constant
(2) No accumulation of mass, energy in system
(3) Properties in each point inside the system do not change with time (may
change with position though)

Mass balance: å m! - å m!
in
in
out
out =0

æ vel 2 ö æ vel 2 ö
Energy balance: Q! + W! + å m! in çç hˆin + in + gzin ÷÷ - å m! out çç hˆout + out + gzout ÷÷ = 0
in è 2 ø out è 2 ø

Common engineering devices in steady-state

Device Purpose ‘Usual’ mass, energy balance

‘Usual’ assumptions
Nozzles, Increase (decrease) the m! in = m! out
(diffusers) velocity of a fluid by æ vel 2 ö æ vel 2 ö
reducing (increasing) the m! in çç hˆin + in ÷÷ - m! out çç hˆout + out ÷÷ = 0
è 2 ø è 2 ø
flow area.
Adiabatic (quick processes)
Not designed to produce/consume power
Fluid experiences no big changes in height
Q! » 0 ; W! » 0 ; zin » zout

Turbines Generate power by m! in = m! out

making a fluid (usually a W! + m! in hˆin - m! out hˆout = 0 ; W! < 0
gas at high pressure) to as
pass through a set of Heat transfer, changes in kinetic and potential
rotating blades. energy usually small when compared with rest
Commonly found in power of terms
plants. Q! » 0 ; velin » velout ; zin » zout
Turbine: http://www.youtube.com/watch?v=Wp4x0KmNEC8
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Device Purpose ‘Usual’ mass, energy balance

Compressors, Used to raise the pressure
pumps of a fluid. Mechanical
power is transferred to the
fluid by a set of rotating
blades. Compressors work
with gases, pumps with
liquid
T Q! » 0 ;
‘Usual’ assumptions
m! in = m! out
W! + m! in hˆin - m! out hˆout = 0 ; W! > 0
Heat transfer, changes in kinetic and potential
energy usually small when compared with rest
of terms
velin » velout ; zin » zout

Throttling Used to reduce the m! in = m! out

isENTHALPic
O
devices pressure of flowing m! in ĥin − m! out ĥout = 0 ∴ ĥin = ĥout
(partially streams
opened valves, No heat transfer; no power; changes in kinetic
porous plugs) and potential energy usually small
Q! » 0 ; W! » 0 ;
velin » velout ; zin » zout
Throttling: http://www.youtube.com/watch?v=sBbNmJakytQ

Device Purpose ‘Usual’ mass, energy balance

Heat Used to ‘heat up’ or ‘cool
exchangers down’ fluids through
(also thermal contact with
condensers,
another fluid, or a heat
evaporators, source/sink, at a different
boilers, etc.) temperature. Can usually
assume isobaric operation
‘Usual’ assumptions
Power, changes in kinetic and potential energy
usually small when compared with rest of terms
W! » 0 ; velin » velout ; zin » zout
Mass, energy balance take different expressions
depending on the selected control volume (use
general expressions and simplify as needed)

Heat exchangers: https://www.youtube.com/watch?v=g6fhEYYM3Uk

Mixing Mix fluids at different Heat transfer, power, changes in kinetic and
chambers temperatures. Can usually potential energy usually small
assume isobaric operation Q! » 0 ; W! » 0 ;
velin » velout ; zin » zout

å m! in = å m! out

å m! in inhˆ - å m! out hˆout = 0

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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
100 35 0.0010060 146.72
700 15 0.0010006 63.650

O O
700 150 0.0010904
O
632.32

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 14

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Estimating values of thermodynamic properties: Given values of two

independent intensive properties for a pure substance, 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 your 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
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PvT behavior, pure substances:

T-v diagram

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

Figure adapted from Koretsky

http://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter2a.html
 17

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

û = x ûv + (1− x ) ûl

H ⎡ kJ ⎤ H ⎡ kJ ⎤
h= ; ĥ = Enthalpy
n ⎢⎣ kmol ⎥⎦ m ⎢⎣ kg ⎥⎦
ĥ = x ĥv + (1− x ) ĥl

App. B textbook: Δĥlv = ĥv − ĥl

Δûlv = ûv − ûl