Thermodynamics of

Materials
MSE 102-0

Course Syllabus
Introduction
Definitions of Thermodynamics
Some Applications of Thermodynamics
Definition of a System
Concept of a State
Equation of State of an Ideal vs. Real Gas

The First Law of Thermodynamics

Various Definitions of the 1st Law
Isochoric Processes
Isobaric Processes
Adiabatic Processes
Isothermal Processes

First Exam

 Entropy, The Second and Third Laws of

Thermodynamics
Definition of Entropy and the 2nd Law
Reversible and Irreversible Systems
The 3rd Law
Entropy of Reactions
Thermodynamics of Surfaces
Surface Free Energy
Surface Tension
Contact Angles
Work of Adhesion

 Eh-pH Diagrams
Definition of Terms and Applications
Construction of Eh-pH Diagrams
Water Stability
Phase Diagrams
Definition of Terms and Applications
The Phase Rule
One-, Two-, Three-Component Diagrams
Final Examination

Introduction
Definitions of Thermodynamics
Some Applications of Thermodynamics
Definition of a System
Concept of a State
Equation of State of an Ideal vs. Real
Gas

Understanding
Thermodynamics
What is Thermodynamics?
What is a Thermodynamic Process?
How does certain processes relate
to the laws of thermodynamics?
Can you use them to determine
the work done or energy produced
by a system?

Brief History of
Thermodynamics
Bone Digester

Bone Digester

(with steam release!)

(high pressure steam)

Denis Papin

Concept of
Engine
Thomas Savery

Vacuum Pump
(1650)
Otto von Guericke

FATHER OF
THERMODYNAMICS!!!
Carnot Engine

Air Pump
(1656)
Robert Boyle and
Robert Hooke

127
YEAR
S

(Carnot Cycle)

Sadi Carnot

Boyles Law

1
P
V

James Joule
(1849)

William Thomson
(1858)

William Rankine
(1859)

Where does the term came

from?
Greek word:
Therme Heat
Dynamis Power
Originally studied to optimize the operation of steam engines

Heat availableMaximum Power

Today the same name is broadly interpreted to include all
aspects of energy and energy transformations, including
power generation, refrigeration, and relationships among
the properties of matter

Definition of
Thermodynamics
Definition #1.
It is the study of the ENERGY
associated with chemical and
physical transformations or
changes which allows
experimentally-determined laws to
be derived from certain basic
principles and predict changes which
have not yet been observed.

Definition of
Thermodynamics
Definition #2.
It is the study of the conversion of
ENERGY into work and heat and its
relation to macroscopic variables
such as temperature and pressure

Thermodynamic Processes
A system undergoes a thermodynamic process
when there is some sort of energetic change within
the system, generally associated with changes in
pressure, volume, internal energy, temperature, or
any sort of heat transfer.
Examples:
1. Cooking using a pressure cooker
2. Inflating a flat tire using an air pump
3. Consumption of fuel by a gasoline engine
4. Boiling/Melting/Freezing

Thermodynamic Processes

Concern of Thermodynamics
The study of thermodynamics is
concerned on the behavior of a
matter or system and its
interaction with its surroundings or
environment

Why Study Thermodynamics in

Materials Engineering?
Materials + Engineering Better
MaterialsDesired Material
Properties

Structure
Composition
Chemical
Reactions and
Other Physical
Treatments

THERMODYNAMI
CS

Why Study Thermodynamics

in Materials Engineering?
Some Examples of Materials Engineering
Activities:
Cement production
Development of metal alloys
Strengthening of material composites
Surface property modification
Failure Analysis
Synthesis of nanomaterials
Production of Semiconductor base
material, etc.

Semiconductor Base
Material

Surface Property
Modification

Applications of Thermodynamics in
Materials Engineering
Aims of Applied Thermodynamics
Determination of the effect of the
environment on the state of rest of a
given system
Shaking an enclosed soda can
Placing a piece of unprotected steel in sea
water
Heating up a copper wire
Exposing NaOH pellets in air

Applications of Thermodynamics in
Materials Engineering
Aims of Applied Thermodynamics
Establishment of the relationships which
exist between the equilibrium state of
existence of the system and the
influences which are brought to bear on
the system
Increase/decrease the temperature
Increase/decrease pressure
Increase/decrease degree of agitation
Etc.

Terms and Definitions

System
- anything that occupies space
- the object of thermodynamic discussion

Surroundings
- Anything else that is outside of the system

Equilibrium
- Balanced forces
- In thermodynamics, the rate of forward
process is equal to the reverse process

Important Concepts
(System)
Permeability of the System
Open
Allows heat and mass to pass through

Closed
Allows heat only

Isolated
Does not allow both heat and mass

Important Concepts
(System)
State of the System
State is a condition/property of a
system:

How
How
How
How

big?
hot/cold?
heavy?
many atoms per square inch?

Can be either Microscopic (Microstate)

or Macroscopic (Macrostate)

Important Concepts
(System)
Microscopic State
Examples:
Masses
Velocities
Positions
Mode of motion

Important Concepts
(System)
Macroscopic State
Examples:
Temperature
Pressure
Volume (i.e. V=V(P,T))
Viscosity
Vapor Pressure
Surface Tension

Important Concepts
(System)
State variables (variables of
State)
Independent of the history of the system
Have 2 types:
1. Extensive Variables (Extrinsic)
mass dependent, additive
Examples: mass, volume, surface area, etc.

2. Intensive Variables (Intrinsic)

not mass dependent
Examples: Temperature, density, refractive
index, etc.

Concept of Equilibrium

- System at rest
- Stable, balanced forces

Concept of Equilibrium
Q1. When is the system in equilibrium?
W

The pressure exerted by the gas on the piston equals

the pressure exerted by the piston on the gas
The temperature of the gas is the same as the
temperature of the surroundings (provided that heat can
be transferred through the wall of the cylinder)

Q2. What happens if we decrease the weight

W?
Pressure inside the cylinder decreases
Volume of the gas inside the cylinder increases
Piston will move up

Q3. Determine what happens if instead of

changing W, we increase the temperature of
the surroundings?

Concept of Equilibrium
State 1
Transition
State 2
Equilibrium1 non-equilibrium
Equilibrium
W

Concept of Equilibrium
An equilibrium state is undisturbed
as long as the system is remained
isolated
A system can change to new
equilibrium due to interaction with
the surroundings
A change in equilibrium is signalled
by a change in its thermodynamic
state
An equilibrium of a system is

Equations of State
Reacting System

Mathematical Expression

P
n

F(x) = ???

Equations of State
Describes the over-all condition of
the System
System considered are in equilibrium
(state variables have values that are
uniform and constant through out the
system
These are path independent (concern
is only on the initial and final states)

Equations of State
Example
Volume (V)
General Formula:
V = (P, T)
V
V

P1
P2

T1
P

T2

Equations of State
Path #1

V1 2 V1 a Va 2
V1 a
Va 2

V1 2

T P
T
V
V

P T T

P1
P2
P

T1
P

T2

Equations of State
Path #1

V1 2 V1b Vb 2
V1b
Vb 2

V1 2

T P
T
V
V

P T T

P1
P2
P

T1
P

T2

Equations of State
Ideal gases
Follow ideal gas law
Particles only interact through elastic
collisions (no energy loss before and
after collisions)
Describe by the equation of state:

PV Nk BT nRT

Where:
P Pressure

kB- Boltzmann constant (1.381X1023J/K)

T Temperature
n amount of gas in moles
R gas constant (8.314J/mol.K)
V - volume

How was an Ideal gas

idealized?
Derivation:
Form Boyles Law (1660):
1
P

From Charles Law (1887):

VT

From Gay-Lusaacs Law (1802):

1 V

V0 T

Boyles Law
(or Boyle-Mariotte Law)

Pressure

1
P
V

T1<T2
T2
T1

Robert Boyle
(1627-1691)

Volume

At constant Temperature!

Charles Law
VT

P1

Volume

P2

Jacques Alexandre
Csar Charles
(1746-1823)

P1<P2

Temperature

At constant Pressure!

Gay-Lussacs Law

Joseph Louis Gay-Lussac

(1778-1850)

Observed that the

fractional increase of the
volume of gas of some
gases are constant
Conducted the
experiment starting at
1 V
o
0 C

V0 T

Gay-Lussacs Law
1 V

V0 T

1/267 = 0.00374 (Gay-Lussac)

1/273 = 0.00366 (Regnault)
P

Where
Vo original volume of gas (at 0oC)

1/273.15 = 0.00366099
-273.15oC
Absolute Temperature!

V
- increase

in volume at constant pressure

P
coefficient of thermal expansion

Combination of Boyles anc

Charles Laws
Boyles Law

1
P
V
PV k1
k1
V
P
At const. T

Charles Law

Recall general equation:

VT
V
k2
T
V Tk 2
At const. P

V
V

P
V

k1
PV V

P2
P2
P

k2
P

V
T

V
V
dP dT
P
T
dV
dP dT

V
P
T
ln V ln P ln T const.
ln V ln P ln T const.
PV
const.( R )
R=0.08205 Li atm/mol-K
T
dV

Values of Gas Constant

Units
(VPT1n1)

Values of R
8.314472(15)

JK1mol1

1.9858775(34)

calK1mol1

8.314472(15)107

ergK1mol1

8.314472(15)

m3PaK1mol1

8.314472(15)

cm3MPaK1mol1

8.31447210-5

m3barK1mol1

8.20574610-5

m3atmK1mol1

8.31447210-2

LbarK1mol1

0.08205746(14)

LatmK1mol1

62.36367(11)

LmmHgK1mol1

62.36367(11)

LTorrK1mol1

6.132440(10)

ft-lbK1g-mol1

1545.349(3)

ft-lbR1lb-mol1

10.73159(2)

ft3psiR1lb-mol1

0.7302413(12)

ft3atmR1lb-mol1

998.9701(17)

ft3mmHgK1lb-mol1

1.986

Btulb-mol1R1

PV Plot of other Gases

T1
T2

T1>T6

T3

Pressure

T4

TCr
n

PCr

Gases tend to conform to

ideal gas laws at higher temp
and low pressures

T5

e
s
ea p
r
ec em
D T

T6

D
C

A
VCr

Molar Volume

Behavior of the PV isotherm

changes as temp decreases
ideal

Non-ideal

Observations
Behavior of different gases varies
from each other
Gases with lower boiling points obey
these laws more closely than those
with higher boiling points
Gases obey the laws more closely at
low pressure

Non-ideal Gases
Do not follow the ideal gas law
Determined by the existence of the
compressibility factor

Compressibility Factor
Compressibility (Z)
- The ability of the substance to be
compressed
- used to describe the deviance in the
thermodynamic properties of the real
(non-ideal) gasPV
from the ideal gas

RT

(For Ideal gas, Z = 1)

Compressibility Factor
The value of Z was derived based on
the experimental data comparing the
it from the change in pressure which
was found to be linear function of P
above at a certain Pressure

Compressibility Factor

Increasing
Temp

Ideal Gas

y = mx + b

Derivation of
Compressibility Factor
Linear equation: y = mx + b
x is Pressure (P)
m is the slope
b is 1 for ideal gas

Z = mP + 1 = PV/RT
Rearranging, for non-ideal gases:
P(V-b) = RT
(where b = mRT)

Gas Particle Interaction

Assumption on ideal gas:
It consist of volumeless non-interacting
particles
Energy of these particles is entirely
translational energy of the motion of its
constituent particles

To simulate conditions for ideal gas,

the following considerations are
needed:
Particles occupy a finite volume

Effect of Volume on
Interaction
Two types of volume:
Molar volume
Volume of the molecule (sphere)

High molar volume

(low molar density, n/V=P/RT)

Low molar volume

(high molar density, n/V=P/RT)

Van der Waals Equation

Has included the volume and
interaction effects for a non-ideal gas
system, represented by the equation:

a
V b' RT
2
V

(For 1 mole of gas)

Where
a/V2 - the correction term of the interactions
V measured volume of gas
b correction factor for finite volume of particles

Van der Waals Equation

a
The correction factor, 2
V
refers to the interaction of the
system particles with each other
and between the walls of the
chamber
Approaching the wall, particles
adjacent to the wall experience
an inward pull

n2a
P 2 V 'nb' nRT (where V ' nV )
V'

(For n moles of gas)

Lower P on the wall

Van der Waals Equation

The correction factor, b

4
3
volume 2r
3

refers to the volume factor which

molecules occupy

(for 2 particles)

This is in accordance to the

observation of 2 colliding
molecules which results in an
exclusion of some volume
2r

1 4
3
volume excluded 2r
2 3

(for each particle)

Van der Waals values

Acetic acid
Acetic anhydride
Acetone
Acetonitrile
Acetylene
Ammonia
Argon
Benzene
Bromobenzene
Butane
Carbon dioxide
Carbon disulfide
Carbon monoxide
Carbon tetrachloride
Chlorine
Chlorobenzene
Chloroethane
Chloromethane
Cyanogen
Cyclohexane
Diethyl ether
Diethyl sulfide
Dimethyl ether
Dimethyl sulfide
Ethane
Ethanethiol
Ethanol
Ethyl acetate
Ethylamine
Fluorobenzene

a
(L2bar/mol2)
17.82
20.16
14.09
17.81
4.448
4.225
1.363
18.24
28.94
14.66
3.640
11.77
1.505
19.7483
6.579
25.77
11.05
7.570
7.769
23.11
17.61
19.00
8.180
13.04
5.562
11.39
12.18
20.72
10.74
20.19

b (L/mol)
0.1068
0.1263
0.0994
0.1168
0.05136
0.03707
0.03219
0.1154
0.1539
0.1226
0.04267
0.07685
0.03985
0.1281
0.05622
0.1453
0.08651
0.06483
0.06901
0.1424
0.1344
0.1214
0.07246
0.09213
0.0638
0.08098
0.08407
0.1412
0.08409
0.1286

Fluoromethane
Freon
Germanium tetrachloride
Helium
Hexane
Hydrogen
Hydrogen bromide
Hydrogen chloride
Hydrogen selenide
Hydrogen sulfide
Iodobenzene
Krypton
Mercury
Methane
Methanol
Neon
Nitric oxide
Nitrogen
Nitrogen dioxide
Nitrous oxide
Oxygen
Pentane
Phosphine
Propane
Silane
Silicon tetrafluoride
Sulfur dioxide
Tin tetrachloride
Toluene
Water
Xenon

a
(L2bar/mol2)

4.692
10.78
22.90
0.03457
24.71
0.2476
4.510
3.716
5.338
4.490
33.52
2.349
8.200
2.283
9.649
0.2135
1.358
1.408
5.354
3.832
1.378
19.26
4.692
8.779
4.377
4.251
6.803
27.27
24.38
5.536
4.250

b (L/mol)
0.05264
0.0998
0.1485
0.0237
0.1735
0.02661
0.04431
0.04081
0.04637
0.04287
0.1656
0.03978
0.01696
0.04278
0.06702
0.01709
0.02789
0.03913
0.04424
0.04415
0.03183
0.146
0.05156
0.08445
0.05786
0.05571
0.05636
0.1642
0.1463
0.03049
0.05105

First Law of
Thermodynamics

Law of Conservation of
Energy
States that energy can be
transformed (changed from one form
to another), but it can neither be
created nor destroyed
The increase in the internal energy
of a system is equal to the amount of
energy added by heating the system,
minus the amount lost as a result of
the work done by the system on its
surroundings.

Internal Energy
It is the energy associated with the state
of the system, denoted by U
It is the total of the kinetic energy due to
the motion of molecules (translational,
rotational, vibrational) and the potential
energy associated with the vibrational and
electric energy of atoms within molecules
or crystals.
It includes the energy in all of the chemical
bonds, and the energy of the free,
conduction electrons in metals.

Internal Energy
w U B U A

q U B U A

(work only)
(heat only)

Internal Energy are state functions.

w work
q heat

(positive if done by the system)

U U B U A q w
dU q w

(over-all)

(for infinitesimal changes)

Internal Energy

w PdV

P1

a
b
c

Pressure

dU q w
w PdV

P2

V1

Volume

V2

Internal Energy
Suppose, U = U(V,T)

U
U
dU
dV
dT
V T
T V
Process examination can be done by making one of the
variables constant:
- Volume
Isochoric
- Pressure
Isobaric
- Temperature
Isothermal
- No heat flow
Adiabatic

Constant Volume Processes

For a system at controlled/constant
V, (Isochore)

PdV 0
dU qv

No work is applied on/by the system,

the contribution is coming only from
the heat flowing in or out of the
system

Constant Pressure
At constant pressure, work is not
2
2
equal to 0.
w P PdV P dV P V2 V1
1

Using the equation for the First Law:

U 2 U1 q p PV2 V1

Rearranging

U 2 PV2 U1 PV1 q p
H U PV

Enthalpy

H 2 H1 H q p

Enthalpy Change

Illustrations
Isochoric (w = 0)
P1

a
b

Pressure

Isobaric w = PdV

P2
PdV
V1

Volume

V2

Adiabatic Process
No heat transfer between the system
and surroundings
Isolated systems (but not
mechanically isolated)
Comes from the Greek roots ("not"), - ("through"), and
("to pass")

Adiabatic Process
Adiabatic Heating

Adiabatic changes in temperature occur

due to changes in pressure of a gas while
not adding or subtracting any heat
General Continuous Formula is given by:

P2V2 P1V1 PV constant

T1
T2
Adiabatic Cooling

Adiabatic processes are achieved

by slow, equilibrium processes
(reversible process)

T, P, V
W

Heat Flow TT1

T1
V1
P1

V1 > V2
P1 < P2

T1
V2
P2

T, P, V
W

No Heat Flow
T1
V1
P1

T2
V2
P2

Derivation of Continuous
Formula
From the First Law of Thermodynamics:
0

U q w
U w

Adiabatic Systems :
no heat transfer

But U=U(T, V)

dU
dT
T V

w
dT

T V

So,

U
dV
V T
U
dV
V T

For ideal gas, dV is 0

U
w
dT CV dT
T V

Derivation of Continuous
Formula
From previous discussions

w pdV
Therefore,

w CV dT pdV
For an ideal gas at 1 mole, we can write p=RT/V thus

RT
CV dT
dV
V
Combining similar terms

CV
R
dT dV
T
V

Derivation of Continuous
Formula

Integrating

T2

V2

CV
R
T T dT V V dV
1
1
T2

V2

CV ln T T R ln V V
T2
V2
CV ln R ln
T1
V1
Taking the exponential form

T2

T1

CV

V2

V1

T2 V2

T1 V1

R
CV

Derivation of Continuous
Formula

For Heat Capacity Discussions, CP - CV = R

T2 V2

T1 V1
Let

CP
, then
CV

Recall from ideal gas law

C P CV
CV

V2

V1

T2 V2

T1 V1

P1V1 P2V2

T1
T2
T2 P2V2

T1 P1V1

CP
CV

Derivation of Continuous
Formula
The equation becomes
P2V2 V2

P1V1 V1

Combining similar terms

P2 V2

P1 V1

P2V
5

3
7

V1 V1

V2 V2

PV

For monoatomic ideal gas

For diatomic ideal gas

1 1

Adiabatic Process
Examples:
A monoatomic ideal gas at room temp
is compressed adiabatically by
increasing the pressure of the system
from 5 atm to 10 atm. What is the
corresponding Temperature change of
the system after compression? How
much volume of the gas is compressed
based on its original volume?

Example
Given:
P 5 atm
1

P2

P2 10 atm
T1 25o C 273.15 25 298.15K

5
3

T2

Solution:

P1

T1

P1V1 P2V2 constant

Get the relationship of T vs P for adiabatic systems:

PV nRT
nRT
V
P

Plug
in

nRT1

P1V1 P2V2 P1
P1
P11 T1 P21 T2

V2

V1

nRT2

P2
P2

P11
T2 T1 1
P2

=393.4113K
(120.26oC)

Assignment
Find CV of the monoatomic gas
If assumed diatomic, compare the
degree of volume change with
monoatomic.
Answer:
c
5
5c
CPV of
monoatomic
gas:
cP V
cV

cP cV R 0.08205 Li atm/deg.mol 8.3144 J/deg.mol

5cV
5 2
cV cV 1 cV R
3
3 3
3
cV R 0.123075 Li atm/deg.mol 12.4716 J/deg.mol
2

Answer:
Degree in change in volume for monoatomic:
P1V1 P2V2
P1 V2

P2 V1
V2 5

V1 10

P1

P
2

3
5

V2
V1

Conclusion:
The degree of volume change
Degree in change in volume for diatomic:for monoatomic gases in an
adiabatic system indicates that
3
it is 8% more compressible
V2 5 7

0.743 ~ 74% of original volume

compared to diatomic gases.
V 10
0.65975 ~ 66% of original volume

Difference: 8%

Monatomi
c gas

CV, m (J/
(molK))

CV, m/R

He

12.5

1.50

Ne

12.5

1.50

Ar

12.5

1.50

Kr

12.5

1.50

Xe

12.5

1.50

Diatomic
gas

CV, m (J/
(molK))

CV, m / R

H2

20.18

2.427

CO

20.2

2.43

N2

19.9

2.39

Cl2

24.1

2.90

Br2

32.0

3.84

Monoatomic gas:
Degrees of freedom f = 3
(all translational)
CV = 3/2R

diatomic gas:
Degrees of freedom f = 7
(translational, vibrational and
rotational)
CV = 7/2R

Isothermal Systems
Systems with constant temperature
(dT=0)
Process undergo such that there is no
change in temperature of the system
Typical set up is a system in contact
with a reservoir or heat bath such
that the change occurs slowly
enough to allow the system to
continually adjust to the temperature
of the reservoir through heat

Typical Set-up of Isothermal

Systems
W

Tchamber = constant
V = decreased
P = increase
Tbath = increased

Tbath

Tchamber

dU q w

For isothermal process,

the change in internal
energy of an ideal gas is
zero.

dU q w 0
q w
dV
w PdV RT
V
2
V
1
RT dV RT ln 2
V
V1
1
V
1
dV RT ln 2
V
V1
1
P
RT ln 1
P2
2

RT
For isothermal process, PV = RT. Therefore:

P1V1 = P2V2

Examples
In an Isothermal system at 10 atm and 25oC, what
is the equivalent energy (q) for an ideal gas if the
piston of the cylinder is displaced by 5cm
V

RT
ln
upwards after W was
decreased? (r = 4 Vcm)
W
2

V1 4 2 100.53 mL
2

V2 4 7 351.85mL
2

V2

V
1

q RT ln

351.85

100.53

0.082057 25 273.15 ln

5 cm

q 30.6488 Li - atm 3105.48 J

2 cm

Heat Capacity
Important for Adiabatic and
Isothermal Systems
It is the ratio of heat and
temperature of a system equivalent
to the amount required to raise/lower
the temperature of the system by 1
degree, denoted
q byqC
C

dT

Note: Concept of heat capacity is not applicable for phase changes

Heat Capacity
2 ways to describe heat capacity:
1. Heat capacity at constant volume
(Cv)
2. Heat capacity at constant pressure
(Cp)

Cp C v

Heat Capacity at Constant

Volume
The derivation of Heat Capacity at
constant volume (CV) is based from
the Isochoric Process where:
dU qV
dU

dT

dT

This gives
dU CV dT

CV
V

Heat Capacity at Constant

Pressure
The derivation of Heat Capacity at
constant Pressure (CP) is based from
the Isobaric Process where:
dH q P
dH

dT

dT

CP
P

This also gives

dH C P dT

Heat Capacity
Heat Capacity is an Extensive property
(dependent on the mass of the system)
For convenience, it is more applicable to
use specific heat capacity (per gram)
or the molar heat capacity (per mole)
of the system which is given by

CP
cP
n
CV
cV
n

Where n is the number

of moles or mass (grams)
of the system, while cp
and cv (lower case letters)
are the molar or specific
heat capacities.

CP vs CV
For most substances, CP is greater in
magnitude than CV
The relationship between Cv and CP
is:
cP cV R
Where R is the gas constant.

Derivation of CP and CV
Relationship
1st Path: 1 1a 2
U11a q P w cP dT PdV
U11a qV w cV dT 0

Isochoric (w = 0)

Integrating
U1 2 U11a U1a 2 0
V2

V1

P1

V2

2 Path: 1 2
U1 2 q w 0
nd

Isothermal (U=0)

Pressure

V1

0 cP dT PdV cV dT
PdV cP dT cV dT

1a

P2

T2
V1

1
T1

Isobaric w = PdV

Volume

V2

T1

T1

T2

T2

T2

T1

T1

PdV cP dT cV dT

cP cV dT
PdV cP cV dT
V2

Computing dU:
U1 2 U11a U1a 2 0

T2

PdV cP dT cV dT

V1

PdV

dV
dT

T2

T1

cP cV

From ideal gas: PdV = RdT

dV/dT = R/P
R
cP cV
P
R cP cV
P

Explanation Why CP>CV

cP and cV are given by the equations below:

cP

P
P

Effect of work to internal energy

(extra energy needed to keep the pressure constant)

Effect of temperature to internal energy

cV

Manipulating:
U
cP cV

P
P

U
U
dV
dT

V
dU
U dV
U

dT

V
dT

P
T
P

But dU

Explanation Why CP>CV

Then

U dV

V T dT

cP cV

U dV

V
dT

cP cV

For ideal gases,

P
V

P
P

V U

From ideal gas (PdV = RdT)

P
cP cV R
cP cV P

Therefore,

cP cV P

Heat Capacity of Solids

For solids (or even liquids), only one type of heat
capacity is considered to have practical usage: c p
This is due to the following reasons:
Particles interact strongly with each other
(dU/dV)P is very large
Energy is much stronger in keeping a specific distance
between atoms at these states such that constant
volume conditions at different internal energies seem
impossible to attain (atoms are much closer to each
other)
Measurements of cV were only done theoretically
through quantum concepts (formulated by Debye and
Einstein) and is comprised of several significant
uncertainties (inaccurate)

Heat Capacity for Solids

From previous equations:
H
cP

V
P

T
P

cV

U
U
dV
dT
V T
T V
dU
U dV
U

dT P V T dT P T

cP >> cV

dU

Empirical Rules
Dulong and Petit (1819) introduced an
empirical rule for the molar heat capacities
of solid elements which is estimated to be
equal to 3R ~2.49 J/mol K
Cv = 3R
Kopp-Neumann (1823) introduced another
rule that at ordinary temperatures, the
molar heat capacity of a chemical
N
compound is approximately
equal to the
c capacities
ci f i of its
sum of the molar
i 1
components

Empirical Rules
Due to difficulty in measuring heat
capacities of solids at constant
volume, it is a normal practice to
measure the variation of the
constant-pressure molar heat
capacity with temperature and
express the relationship analytically

Empirical Rules
Data were gathered based on experimentally
measured variation of the constant-pressure
molar heat capacity
It was found out that the Molar heat
capacity varies with temperature
A function was used to derive the
value of the molar heat capacity
which is in the form:

cP a bT cT 2 J/mol K

Empirical Representation of
Heat Capacities
Example: -ZrO2 (Temp range: 298K - 1478K)
a = 69.62
b = 7.53 x 10-3
c = - 14.06 x 105
Therefore, CP

cP 69.62 7.53 10 3 T 14.06 105 T 2

Note:
Each set of values or expression is applicable only to a
certain temperature range, which is most probably working
on the same phase of the system

Heat Capacity Exercise

What is the value of CP of a 500g ZrO at 100oC?
MW: Zr = 91.22 g/mol
O = 16 g/mol
cP 69.62 7.53 10 3 T 14.06 105 T 2 J/mol K

Ans. cP 69.62 7.53 10 3 100 273.15 14.06 105 100 273.15 2

cP 62.332 J/mol K

500 g
62.332 J/mol K 290.6744 J/K
C P ncP
91.22 16 g/mol

Application of Empirical
Heat Capacity
Computation of Enthalpy (H)
For a closed system of fixed
composition, with a change in temp (T1
T
T2) at CONSTANT PRESSURE
2

H H T2 , P H T1 , P cP dT
T2

c dT

T1

T1

The term
is equal to the area
under the plot of CP vs T

Example
Determine value of H of 1 mole of
an -ZrO with the Cp described on the
T = 412 K
Cp vs T
plot
below:
T = 621 K
80.0000
1
2

70.0000
60.0000
50.0000
40.0000
30.0000
20.0000
10.0000
0.0000

T2

Cp (J/mol K)

H cP dT
T1

Temperature (K)

Solution
T2

H cP dT
T1

T2

14.06 105
dT
H 69.62 7.53 10 T
2
T

T1
3

7.53 10
2 14.06 10
H 69.62 T
T2

2
T

T2

T1

7.53 10 3 2
1
2
5 1
H 69.62 T2 T1
T2 T1 2 14.06 10

2
T2 T1

7.53 10 3
1
1
2
2
5
H 69.62 621 412
621 412 2 14.06 10

2
621
412

H 14550.58 812.85 2297.062 13066.368 J 13.066 kJ

 HT1 and HT2 are change in

enthalpies that do not involve any
change in temperature
They contribute to the total heat of
the reaction but are not dependent
on temperature
Existence of such indicates a phase
change on the system

Review: Heat of Formation

"standard heat of formation" of a
compound is the change of enthalpy that
accompanies the formation of 1 mole of a
substance in its standard state from its
constituent elements in their standard
states (the most stable form of the
element at 1 bar of pressure and the
specified temperature, usually 298.15 K or
25 degrees Celsius) symbol is Hfo
Heat of formation for elements is equal to
ZERO.

Standard Computation

For a certain reaction at 298 K:

M(solid) + 1/2O2(gas) MO(solid)

Heats of Formation at 298K for:

M = HM(solid)298K
O = HO(gas)298K
MO = HO(gas)298K
H 298 nMO H MO ( s ) 298 ( Products) (nM H M ( s ) 298 nO H O ( g ) 298 ) reactants
H 298 H MO ( s ) 298 ( H M ( s ) 298
H 298 H MO ( s ) 298

1
H O ( g ) 298 )
2
0
0 Both are in elements at 298K

For reactions not at 298 K, a different approach is used.

Heat of Reaction
It is the heat involved (evolved or
absorbed) when reactants react
completely to produce products
Denoted by Hrxn
o
o
o
H rxn
H products
H reactants

Other forms of Heat of

Reaction
Heat of Combustion burning
reaction with oxygen (usually forming
CO2 or H2O)
Heat of Solutions heat involved in
dissolving substances
Heat of Transformation includes
fusion, vaporization, sublimation,
transition

Hess Law
The law states that the enthalpy
change for any chemical or physical
process is independent of the
pathway or number of steps required
to complete the process
The total change in enthalpy is just
the sum of all the enthalpy changes
involved in each process step

Kirchoffs Law
The heat of reaction at any given
temperature may be calculated if the
heat capacity of products and
reactants as well as heat of reactions
at one temperature are known