Chemical Engineering

Thermodynamics

 Textbooks
1.

Koretsky, M.D. (2004) Engineering and Chemical

Thermodynamics, 1st edition, John Wiley &Sons.
(ISBN: 0-471-38586-7)
(New Edition) Koretsky, M.D. (2013)
Engineering and Chemical Thermodynamics,
2nd edition, John Wiley &Sons.

2. Smith J.M., Van Ness H.C., Abbott M.M.(2004)

Introduction to Chemical Engineering

Thermodynamics, 7th Ed. Mc-Graw Hill (ISBN:
0072402962)
2

Marks Allocation
COURSE WORKS:

1 Test: 20 %, Assignment: 20 %
FINAL EXAMINATION: 60 %
PASSING MARK:

50 %

CONSULTATION HOURS:
Wednesday: 9 am 11 am; 2 pm 4 pm
*please make appointment at least 2 days prior to the

consultation

Chapter 2
The First Law of Thermodynamics
Learning Objectives
Thermodynamic property, extensive and intensive
properties
Introduce the laws of thermodynamics and the forms
of energy
Themochemical data for internal energy & enthalpy
Describe the energy changes associated with sensible
heat, latent heat, and chemical reaction on both a
macroscopic and a molecular level.
Calculate their enthalpy changes using available data
such as heat capacity, enthalpies of vaporization,
fusion and sublimation, and enthalpies of formation.

Classification of
Thermodynamics properties
Extensive properties (K)

Depend on the mass/size of the system

Example: V, G, U, H, S
Intensive properties (k)

Does not depend on the mass/size of the system

(1) Intensive molar ( =

Example: v, g, u, h, s
(2) Intensive specific ( =
Example: , , , ,

Energy
(1) Macroscopic kinetic energy (Ek)
energy associated with the bulk (macroscopic) motion
of the system as a whole
(2) Macroscopic potential energy (Ep)
energy associated with the bulk (macroscopic) position
of the system in a potential field
(3) Internal energy (U)
energy associated with the motion, position, and
chemical-bonding configuration of the individual
molecules of the substances within the system.
7

(4) Enthalpy (H)

associated with both internal energy and flow of work
Formula: h = u + pv
intensive
Unit: kJ/kg
or H = U + PV
extensive
Unit: kJ
(5) Entropy (S)
Clausius: Heat absorbed during reversible process
Formula: =

intensive

Unit: kJ/kg.K

Boltzmanns molecular view: Degree of disorder in a

system
8

+Q

-Q
Q given off by
the system

SYSTEM

Q received by
the system

(6) Heat (Q)

A form of energy transferred between the surrounding
and the system due to the driving force of temperature
difference
A process in which there is no heat (Q = 0) is called an
adiabatic process
(7) Work (W)
A form of energy transferred across the boundary
associated with a force acting through a distance
* W and Q are process functions!
(i.e., their magnitudes depend on the path followed during a process as well as the end states)

Law of Thermodynamics
(1) Zeroth Law of Thermodynamics:
Two bodies are in thermal equilibrium with a third body,
they are also in thermal equilibrium with each other

(2) First Law of Thermodynamics:

Conservation of energy principle i.e. energy cannot be
created or destroyed

10

 The law of conservation of energy

+Q

+W
SYSTEM
Ek
Ep
Et
U

SURROUNDINGS

BOUNDARY

For a closed system undergoing a thermodynamic

process, the energy balance equation

+ + = +
11

(3) Second Law of Thermodynamics:

It is impossible to build an engine which operating in a
cycle can convert all the heat it absorbs into work.
Kelvin and Planck
Heat cannot be caused to flow from a cooler body to a
hotter body without producing some other effect.
Clausius
(4) Third Law of Thermodynamics:
The entropy of a perfect crystal is zero at a temperature
of absolute zero
12

Heat Capacity: Cv and Cp

Heat capacity at constant volume, cv

( )

sensible heat:
sense the result
of the heat input
with the
thermocouple

at constant volume

(2.50) (2.24)
u=q+w
u=q
(closed system, const v)

Figure 2.10 Schematics of the experimental determination of heat capacity.

(a) constant-volume calorimeter to obtain cv
13

Heat capacity at constant volume, cv

By taking the slope of the curve as a function of temp,

cv = cv (T)
Fit the data to a polynomial expression
cv = a + BT + CT2 + DT-2 + ET3

(2.51)(-pg. 68)
(2 .52) (2.25)

Then, we can find u by integration

u =

2

1

2
1

a + BT + CT2 + DT2 + ET3 (2.53)(2.26)

Heat capacity should only be used for temperature

changes between the same phase.

14

Heat capacity at constant pressure, cp

=

( )

at constant pressure

(2.58) (2.29)
u=q+w
u=q-Pv or u+(Pv)=q
(Pv)= Pv+vP =Pv
h = q (closed system, const v)

Figure 2.10 Schematics of the experimental determination of heat capacity.

(a) constant-pressure calorimeter to obtain cp
15

Heat capacity at constant pressure, cp

Fit the data to a polynomial expression

cp = A + BT + CT2 + DT-2 + ET3

(2 .59) (2.30)

The parameters A, B, C, D, and E of some ideal gasses are

reported in Appendix A.2.

Heat capacity parameters at constant pressure of some
liquids and solids are reported too.

16

Relationships between cpandcv

cp cv
=

liquids and solids

(2.60) (- pg. 71)

(+)

( ) = [
] = ( ) +( ) = ( ) +

( ) =
= ( )

cp= cv + R

for ideal gases

(2.63) (- pg. 71)

17

Mean Heat Capacity,

Definition: The average of cpbetween two temperatures.
It is usually reported between 298 K and a given

temperature, T.

h = (T 298)

(2.64) (- pg. 71)

Solving for :

298

298

(2.65) (2.33)

18

EXAMPLE 2.6 (2.7)

Heat Input Calculations Using Different Data Sources
Consider heating 2 moles of steam from 200 oC and 1
MPa to 500 oC and 1 MPa. Calculate the heat input
required using the following sources for data:

(a) Heat capacity

(b) Steam tables

19

SOLUTION
(a) At constant pressure, heat input required is
q = h or Q = nh
Assume water is ideal gas, heat capacity values given
in Appendix A.2
5

0.12110
= A + BT + DT2 = 3.470 + 1.450 103 +

2
By using the definition of heat capacity,
0
0
h=

2

1

2
1

A + BT + CT2 + DT2 + ET3

773
2
= [ + ]473
2

h = 8.314 3.470 300 + 0.735103 (7732 4732 ) 0.121105

1
773

1
473

= 10,991 J/mol

Q = nh = 2(10,991) = 21,981 J

20

(b) From steam tables, Appendix B.2:

1 (at 1 MPa, 200oC) = 2827.9 kJ/kg
2 (at 1 MPa, 500oC) = 3478.4 kJ/kg

= 2 -1 = 650.5 kJ/kg
Molecular weight for water, MWH2O = 0.018 kg/mol
Q = m
= (2 mol)(0.018 kg/mol)(650.5 kJ/kg)(103 J/kJ)
= 23,418 J
The answer for part (b) is approximately 6% higher

than for part (a). At 1 MPa, water is not an ideal gas

21

EXAMPLE 2.7 (2.8)

Determination of Mean Heat Capacity for Air
Use the data available in Appendix A.2 to calculate the
mean heat capacity cp, for air between T1 = 298 K and T2
= 300 to 1000 K, in intervals of 100 K.

22

SOLUTION
TABLE E2.8 Calculated Values for Mean Heat Capacity
of Air at Different Temperatures
=

2
1

A + BT + DT2

298

= [ + 2 ]298
2

298
=
=
( 298)
298

Appendix A.2:
Heat capacity for air:
A = 3.355;
B = 0.575x10-3;
C = -0.016x105

23

Latent Heats
Definition: The change of enthalpy during a phase
transition at constant pressure (Heat absorbed as
substance A changes phase)
(1) Enthalpy of vaporization, hvap = hv - hl
The enthalpy of the vapor minus the enthalpy of the
liquid
(2) Enthalpy of fusion, hfus = hs - hl
The change in enthalpy from the liquid phase to the
solid phase
(3) Enthalpy of sublimation, hsub = hv - hs
The change from the solid phase to the vapor phase
24

25

Calculation of hvap, T at any T

Step 1: Change in enthalpy of the liquid from T to Tb
Step 2: Vaporize the liquid at the Tb
Step 3: Change in enthalpy of the vapor from Tb to T

Figure 2.12 Hypothetical path to calculate hvap at temperature T from data

available at normal boiling point, Tb and heat capacity data.

where

26

EXAMPLE 2.11 (2.10)

Determination of Heat Required to Evaporate
Hexane
10 mol/sec of liquid hexane flows into a steady-state
boiler at 25 oC. It exits as vapor at 100 oC. What is the
required heat input to the heater. Take the enthalpy of
vaporization at 68.8 oC to be
hvap, 68.8 oC = 28.88 [kJ/mol]

27

SOLUTION:
Hexane (25oC 100oC)
hvap, 68.8 oC= 28.88 kJ/mol
Heat-transfer rate, = (2 1 )

Enthalpy change involves

(1) sensible heat bring hexane (l) to boiling point;
(2) enthalpy of vaporization (Latent heat)
(3) sensible heat to bring it to vapor state of 100oC
2 1 = 1 + 2 + 3
l,25oC 68.8oC

vap, 68.8oC

v,68.8oC 100oC

28

h1 =
h2 =

342

23.695 8.314 = 8668

298.2

373.2
2
(
+

)
342

= 8.668 /

53.722103
8.314[3.025(373.2-342)+
(373.22 -3422 )
2
6
16.79110
(373.23 3423 )]
3

= 5.20 kJ/mol
= (2 1 ) = (10 mol/s)(8.668 + 28.88 + 5.20)kJ/mol

= 427 kJ/s

29

Enthalpy of Formation, hf

Definition: Enthalpy difference between a given molecule and

the reference state (pure elements in their stable form at 298 K

and 1 bar)
hf

Elements Species i

(2.69) (-pg. 82)

The enthalpy of formation of a species containing only one

element, as it is found in nature, is identically zero, eg. H2, O2

H2(g) + O2(g) H2O(l)

(2.70) (-pg. 82)

The value for the enthalpy of formation for this reaction is

found in Appendix A.3.2 (p.503) (pg. 646)
Water hof,298 = -285.83 kJ/mol (phase : L)
Water hof,298 = -241.82 kJ/mol (phase: G)

30

Enthalpy of Reactions, hrxn

Definition: Amounts of energy can be absorbed or
liberated during chemical reactions

h1: Reactants elements

h2: Elements products
Note: Stoichiometric coefficients
Reactants are negative
Products are positive

31

 Equating the 2 paths yields

horxn298 = h1 + h2 = i (hof,298)i + i (hof,298)i

reactants

= i (hof,298)i

products

(2.71) (-pg. 83)

hrxn can be determined by scaling each species hf by

its stoichiometric coefficient

horxn = ih0i = i (hof)i

(2.72) (2.35)

Enthalpy of formation data can be found in Appendix

A3
32

EXAMPLE 2.12 (2.13)

Determination of Enthalpy of Reaction
Calculate the enthalpy of reaction at 298K for the following
reaction:
SOLUTION:
Enthalpy of formation from App. A.3 & Eq (2.72) (2.35)
0

(hof,298)H2 = 0
The form hydrogen
takes at 298 K and 1 bar.

ho298 = (-393.51) + 3(0) (241.82) ( 200.66)

= 49.0 kJ/mol
h is positive = Reaction is endothermic

33

Example 2.13 (2.15)

Adiabatic Flame Temperature Calculations
Propane enters an adiabatic constant-pressure
combustion chamber at 25oC. It is mixed with a
stoichiometic amount of air. Assume complete
combustion and that the carbon distribution in the
product stream contains 90% CO2 and 10% CO. What is
the exit temperature?

34

SOLUTION:

Figure E2.13B Hypothetical path for

calculation of enthalpy in complete
CO2, CO, N2,
combustion of propane.
HO
2

35

 Using a basis of 1 mol C3H8, chemical reaction for CO2 production

The hrxn can be found based on the reaction stoichiometry given:

Using the values from Appendix 3

Using a basis of 1 mol C3H8, chemical reaction for CO production

The carbon distribution in the product stream contains 90% CO2 and 10% CO,

we multiple the 1st reaction by nIC3H8 = 0.9 and the 2nd reaction by nIC3H8 = 0.1.
The total enthalpy reaction is:
36

 The balanced chemical reactions are

The carbon distribution are 90% CO2 and 10% CO, thus, the
species concentration are

An energy balance on the closed system at constant pressure

37

Appendix A.2 Heat capacity data

T2 is found to be
T2= 2345 K
38

Tutorial 1
Problems:
No. 2.9, -, 2.49, 2.53, 2.54, 2.55

(Koretsky, M.D. (2004) Engineering and Chemical

Thermodynamics, 1st edition, John Wiley &Sons)
No. 2.23, 2.55, 2.74, 2.78, 2.79, 2.80

(Koretsky, M.D. (2013) Engineering and Chemical

Thermodynamics, 2nd edition, John Wiley &Sons)

39