Four Types of Systems

1. Open system exchange of energy and matter occurs

with its surroundings
2. Closed system exchange of energy may occur but no
transfer of matter occurs between the system and its
surroundings
3. Thermally isolated system no exchange of energy (in
the form of heat) takes place
4. Mechanically isolated system no work is done in the
system or by the system
See ATKINS
State of a system can be defined completely by
observable macroscopic properties of matter known
as the variable of state
Pressure,
Volume,
Temperature, and
Composition

Used to specify the state of a thermodynamic system
and their values depend on the conditions or the
state of a thermodynamic system.
i. Extensive variables are proportional to the amount of the
matter (volume, area, mass, heat capacity, free energy,
entropy and enthalpy)
ii. Intensive variables are independent of the amount of
matter (temperature, pressure, density, chemical
potential(measure of reactivity of the system) and
viscosity.
Any two of the variable of state can be
sufficient to fix the state.

Equation of State
identifies the minimum number of
variables needed to define the system.
Variables that can be controlled during
experiments (T and P)

Mass (both extensive)
Volume
Boyles Law (Robert Boyle)
Pressure Volume relationship at constant
temperature
P o (1/V)
T

Charles Law
Volume-temperature relationship
V o (T)
P

Joseph Gay-Lussacs Law
Coefficient of thermal expansion, o, as the fractional
increase, with temperature at constant pressure, of
the volume of a gas
At -273.10C the volume of gas becomes zero, all
motions stop at this temperature
o = (1/V
o
)(dV/dT)
P
= CTE ; V
o
=volume of gas at 0
o
C


Combination of Boyles, Charles and Gay-
Lussacs Law
PV=nRT
Boyles Law
P
o
V(P
o
, T) = PV(T, P)
Charles and Gay Lussacs Law
V(P
o
, T
o
) = V(P
o
, T)
T
o
T
P
o
V
o
= PV = Constant =0.08205 L-atm/mole K
T
o
T
From Avogadros hypothesis, volume of 1
mole of all gases at STP is 22.414L.
R = 0.08205 L-atm/mole K
= 1.987 cal/mole K
= 8.3144 Joules/mole K
Ideal-gas equations assumptions are not
valid when dealing with real gases.
Applicable assumptions are:
a. Volume of molecules may not be negligible in
relation to the volume occupied by the gas
b. Attractive forces between molecules may not
be negligible
P+ P = P + a
V
2















Correction term proportional to:
a. Number of molecules striking
unit area of wall per second at
any instant
b. Number per unit volume of
molecules
Cohesion pressure-
Measure of attractive
force of molecules in
the bulk of the gas
P + a (V-b) = RT
V
2


pressure & volume correction
All molecules have a particular diameter
or volume which is equal to four times
the actual volume of the molecules
according to van der Waals because
repulsive forces occur where they
approach very closely
b, correction factor for ideal volume
occupied by the molecule in the container
A. Various Definitions
B. Forms of Energy
C. Statement of the First Law of Thermodynamics
D. Reactions at Constant Volume and Constant
Pressure
E. Adiabatic Process
F. Isothermal Transformation

A. Various Definitions
Principle of conservation of energy
i. Total amount of energy of an isolated
system remains constant but may change
from one form to another
ii. When an amount of energy of one form
disappears, an equivalent amount of
energy of other forms appear
iii. Energy cannot be created or destroyed
a. Internal Energy
Comes from atom and electron movement
Measure of energy stored in the bonds
translational,
vibrational,
rotational and
electronic effects
b. Work
Interaction between a system and its surroundings
Mechanical
Gravitational
Surface tension
Electrical
Magnetic, etc

+W system has done work on the
surroundings
-W work done on the system
Sample Problem:
Six moles of an ideal gas at 100C undergo isothermal
reversible expansion against a constant external pressure of
3.5 atm in a piston-cylinder apparatus. The volume of the gas
is increased by a factor of 450%. Compute the work
performed as a result of the expansion.

Solution:
Initial total volume (V
1
)
V
1
= 6*8.3144*373.16 = 52.492 x 10
-3
m
3

3.5* 101,325

V
2
= 4.5 * V
1
= 236.214 x 10
-3
m
3

W=}
V1

V2
PdV = P( V
2
-V
1
) = 3.5*101,325(236.214-52.492) x 10
-3
m
3
W= 65,155 J







c. Heat, Q
i. Form of energy mainly due to temperature
ii. Method of energy transfer to an assembly which are not
observable as macroscopic work
iii. Usually produces a rise in temperature when in enters a
system; flows from high to low temperature body
iv. Irreversible process

Calorie( = 4.184 J/cal)
amount of heat required to raise the temperature of 1
gram of water from 14.5 to 15.5C at 1 atm pressure.

Q=C T
+ Q heat is added to the system or
when it crosses the boundary
from the surroundings into the
system
- Q heat flowing out of the system
into the surroundings
2. A copper slag whose mass m
c
is 75 g is heated in a laboratory oven
to a temperature of 312C. The slag is then dropped into a glass
beaker containing a mass m
w
=220g of water. The effective heat
capacity C
o
of the beaker is 45 cal/K. The initial temp T
i
of the water
and the beaker is 12.0C. What are the final temperatures T
f
of the
slag, the beaker and the water?

Heat capacity =mc
Q
w
= m
w
c
w
(T
f
-T
i
)
Q
b
= m
b
c
b
(T
f
-T
i
)
Q
c
= m
c
c
c
(T
f
-T
c
)
Q
w
+ Q
b
+ Q
c
= 0
m
w
c
w
(T
f
-T
i
) + m
b
c
b
(T
f
-T
i
) + m
c
c
c
(T
f
-T
c
) = 0



C
c
=0.092 cal/gK
C
w
=1.00 cal/gK
T
f
=

c c b w w
i w w i p c c c
f
c m c c m
T c m T c T c m
T
+ +
+ +
=
W (joules)
1 cal =4.186 J
1 Cal = 1000 cal

Q= mcAT
Q= amount of heat needed to raise temperature by AT
m= mass of the body
c= heat capacity; characteristic constant of a given body
Q= nMcAT
n= number of moles
M= molecular mass
Q= nCAT
C= molar heat capacity

Example:
1. How much heat is needed (a) to raise the temperature of 725g of
lead from room temperature (293 K) to its melting point (602 K)?
c
lead
=128 J/kg-K
Q = mcAT
= 0.725 kg (128 J/kg-K) (602-293 K)
Q = 2.87 x 10
4
J = 28.7 KJ

Internal energy (AU)
molar heat, work,
Q W



U= Q-W
Q= molar heat absorbed by a system
W=work performed per mole on or by a system
AU increased
Work performed on the system
Heat transferred into the system
AU decreased
Work performed by the system
Heat transferred from the system
System
Energy, U
Isochoric Process AU= Q
W=0; No work done on and by the system
Isobaric Process AU= Q-PAV
Work done on the system because of volume
change (at constant pressure)

Sample problem:
When 1 g-atom of pure iron is dissolved in dilute HCl at 18C, the
heat liberated is 87.03 kJ. Calculate the energy change (AU)
of the system.

Solution:
Fe + 2H
+
H
2(g)
+Fe
2+
AU= Q-PAV PAV= nRT AU= Q-RT ;

Heat is liberated:
AU= -87.03 kJ-2.415kJ=-89.44kJ
At constant volume
Q
V
=C
V
AT AU= C
V
AT
if C
V
is not constant: AU=Q
V
=} C
V
TdT

At constant pressure
Q
P
=C
P
AT AU= q
p
-PAV
(U
2
+PV
2
) - (U
1
+PV
1
)=q
p

H=U+PV for constant pressure only
H
2
-H
1
=
AH=C
P
AT =} C
P
TdT
For 1 mole of gas
C
P
-C
V
=nR

Constant Volume
P
1
V
1

= P
2
V
2

=constant
Constant Temperature
1

1 2
2
1
1
2
exp
ln ln

|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
= =
nRT
W
P P
P
P
RT
V
V
nRT Q W
1. Liquid Cd boils at 760C, 1 atm pressure.
The heat of evaporation, AH
ev
is 23.87
kcal/mole. Calculate the incremental
change in internal energy
accompanying volatilization of 1 mole
of liquid Cd at the boiling temperature.
AH = AU + PAV

A. Definition
B. Thermodynamic Relations Involving
Entropy
Entropy-measure of state of order and disorder of a system
dU=TdS-PdV
*dS is independent of the path
a. Entropy in Isothermal
phase transition

b. Entropy calculations when temperature changes
1. Constant pressure




2. Constant Volume
|
.
|

\
|
A
= A
T
H
S
Tr
Tr
( ) T d C S
P
T
T
ln
2
1 }
= A
T d
T
C
S
V
T
T
}
= A
2
1
Entropy changes for irreversible processes






Entropies in the reaction can be calculated as follows:








) , (
) , (
) , ( ) , (
) , ( ) , (
) , ( ) , (
) , ( ) , (
1
1
,
, .
,
) 3 (
) 2 (
) 1 (
T s
T l
T s T l
T s T l
T s T l
T s T l
A A
A A
A A
A A
A A
l p m
p m p m
p m l

AS
1
AS
2
AS
3
AS
syst

( )
( )
( ) ( )
p m
f
T
T
s P l P
syst
T
T
s P
p m
f
T
T
l P
T
H
dT
T
C C
S
dT
T
C
S
T
H
S
dT
T
C
S
p m
p m
p m
,
3
,
2
1
,
1
1
,
,
1
A

= A
= A
A
= A
= A
}
}
}
Sample Problem:
Calculate the entropy changes of a system and
surroundings for the case of the freezing of
supercooled liquid silver at 800C. The melting point
of silver is 961 C and the heat of fusion is 2.69
kcal/mole. (H
F
=2690)
Ag
(l,1073K)
Ag
(s,1073K)

1. Ag
(l,1073K)
Ag
(l,1234K)
AS
1
=} (C
P(l)
/T) dT

2. Ag
(l,1234K)
Ag
(s,1234K)
AS
2
=-AH
f
/T
m,p
3. Ag
(s,1234K)
Ag
(s,1073K)
AS
3
=} (C
P(s)
/T) dT









( ) | |
molK cal S
x x S
dT T x x T S
syst
syst
syst
/ 20 . 2
18 . 2
1073
1
1234
1
10 36 . 0 * ) 2 ( ) 1073 1234 ( 10 04 . 2
1073
1234
ln 21 . 2
1234
2690
10 36 . 0 10 04 . 2 09 . 5 30 . 7
2 2
5 3
1234
1073
3 5 3 1
= A

|
.
|

\
|
+ = A
= A

}
To solve for the AH of the surroundings,
the heat of fusion at 800C has to be
calculated as follows:

( ) | |
molK cal S
molK cal S
mol cal H
x x H
dT T x T x H
univ
surr
f
syst
f
syst
syst
f
/ 33 . 0 53 . 2 20 . 2
/ 53 . 2
1073
42 . 2717
/ 2717
2690
1073
1
1234
1
10 36 . 0 ) 1073 1234 ( 10 04 . 2 * 5 . 0 ) 1073 1234 ( 21 . 2
2690 10 36 . 0 10 04 . 2 09 . 5 30 . 7
) 1073 , (
5 2 2 3
) 1073 , (
1234
1073
2 5 3
) 1073 , (
= + = A
= = A
= A

|
.
|

\
|
+ = A
= A

}
A. Entropy at Standard Zero
B. Third Law of Thermodynamics
C. Entropy of Reactions
D. Entropy of Reaction with
Variation in Temperature
All substance have the same entropies at absolute zero
temperature
Third law of thermodynamics:
The entropy of any homogeneous substance which is in
complete internal equilibrium may be taken as zero at 0K.
Entropy of Reaction
AS
298(rxn)
=nS
298(products)
-nS
298(reactants)
Example:
2Al+3/2 O
2
Al
2
O
3
at 298K
S
298(Al)
=28.33J/mol K
S
298(O2)
= 205.02J/mol K
S
298(Al2O3)
=50.90 J/mol K
AS
298(rxn)
=50.90-2*28.33-(3/2)*205.02=-313.29 J/mol K
= AS
formation(298)








For processes at temperature combinations other
than T=298K and T=T K, the general equation is as
follows:

dT
T
C
S S
T
T
p
T rxn T rxn
}
A
+ A = A
2
1
1 2
) ( ) (
A. Heat Capacity and Heat Content
B. Enthalpy or Heat Content


C. Heat of Formation
D. Heat of Transformation
E. Heat of Reaction
F. Hess Law
G. Variation of Enthalpy Change With Temperature
H. Adiabatic Flame Temperature
I. Helmholtz Free Energy
J. Calculation of Free Energy Change
K. Gibbs free energy and the Equilibrium Constant
+ AH exothermic, evolves heat
-A H endothermic, requires heat
1. Given: T =298 k, P=1atm and
a. W
(s)
+O
2(g)
WO
2(s)
AH
f
= -560.7 kJ/mol
b. 3WO
2

(s)
+O
2(g)
W
3
O
8(s)
AH
rxn
= -550.2 kJ/mol
c. W
3
O
8(s)
+1/2 O
2(g)
3WO
3(s)
AH
rxn
= -278.3 kJ/mol
Find enthalpy change for the reaction producing WO
3(s)


2. The standard enthalpies of formation of several
minerals at 968K are as follows:
a. Al
6
Si
2
O
13
(mullite) AH
f(968K)
= 42.2kJ/mol
b. Al
2
O
3
(corundum) AH
f(968K)
= 31.8kJ/mol
c. SiO
2
(quartz) AH
f(968K)
= -15.3kJ/mol
Calculate AH for the production of mullite from
corundum and quartz at 968 K.

PHASE CHANGE
always accompanied by release or absorption of
heat

Phase change from solid to liquid
Q o m, Q=L
f
m
L
f
=latent heat of fusion;
constant character of body
L
c
=latent heat of combustion;
L
s
=latent heat of sublimation;

Phase change from liquid to gas
Q=L
v
m
L
v
=latent heat of vaporization;
constant character of body
* Steam is hotter due to the temperature it absorbed in the process of vaporization

Heats of fusion and vaporization








reversible - temperature used in phase
change
Temperature
Time
solid state
liquid state
gas state
Substance Melting Point
(C)
L
f

(J/kg)
Boiling Point
(C)
L
v

(J/kg)
H -253.91 58.6 X 10
3
252.89 452 X 10
3

O
2
-218.79 13.8 X 10
3
183.0 213 X 10
3

H
2
O 0.00 334 X 10
3
100.00 225 X 10
3

Ag 960.80 88 X 10
3
2193 2336 X 10
3

Example:
How much heat is needed
(a) to raise the temperature of 725g of lead
from room temperature (20C or 293K) to its
melting point?
C = 1285 /kg K
T
m
= 602 K
Q = mc (T
f
-T
i
)
= 2.87 x 10
6
J
Q= 287 kJ
(b) How much additional heat is required to
melt the lead at its melting point?
Q= L
f
m
L
f
= 23.2 J/ kg
Q=16.8 kJ

3. Calculate the standard heat of formation of solid
PbO from liquid Pb and O
2
gas at 527C. The
melting point of lead is 327C and its latent heat of
fusion is 1.15kcal/mole. The molar heat capacity at
constant pressure of liquid Pb is
C
P(Pb(l))
=7.75-0.74x10
-3
Tcal/molK.
AH
f(PbO,298)
= -52.4 kcal/mol
C
P(PbO)
=10.6 + 4.0x10
-3
T cal/molK.
C
P(Pb)
= 5.63 + 2.33x10
-3
T cal/molK.
C
P(O2)
=7.16 + 1.0x10
-3
T 0.4 x10
5
T
-2
cal/molK.

Maximum attainable temperature of
combustion products when reaction occurs
completely at 298K under adiabatic
conditions.
Reaction where heat neither enters or leaves the
system
Combustion of fuel in a confined system
Fuel + oxidant
(at 298)
combustion
products(at very high temp, Tm)


This rection can be performed in two imaginary steps:
1. fuel + oxidant
at

298
combustion products
at 298

2. Combustion products
at

298
combustion products
at Tm


Reaction in 1 is always exothermic(combustion reaction)
Available thermal energy is used to heat up combustion
products from 298 to T
m


Depend on the initial and final states of the system
When P and T are constant
G= dH TdS
Reaction at constant temperature and
volume
F=Q-TS=U-TS (Helmholtz Free Energy)
Independent of the path taken
At constant T and P:
AG = 0 reaction is at equilibrium
A G<0 spontaneous reaction in the specified direction
AG>0 not spontaneous in the specified direction
DC
p
~0, thus AG
T
= AH
298
-T AS
298

For a system in equilibrium
Rate of forward reaction=rate of backward
reaction
K
eq
=K
1
/K
2 ;
K
1
& K
2
are specific rate constants
Activity, a
i
=
i
C
i

i
=activity coefficient characteristic of a given ionic
specie

C
i
=concentration of specie expressed in moles
a
i
pure substance =1

i
ionic specie in very dilute solutions =1
a
i
=partial pressure; for gases at low pressures

K
eq
=exp(AG/RT)
Vant Hoffs Isochore
d ln K
p
=AH
dT T
2
K
p
= - AH + constant (at any temp)
RT
Clausius-Clapeyron Equation
d ln P
A
= L
e

dT RT
2
P
A
=vapor saturation pressure


1. Calculate the vapor pressure of Mn in
molten steel (1600C) if L
e
=226 kJ/mole
at 2095 C.
Daltons Law
The total pressure P
t
of an ideal gas mixture is
equal to the sum of the pressures exerted by
each component
AG
1
=RT lnP
i
=RT ln(X
i
P
T
)
Le Chateliers Principle
When a system, which is at equilibrium, is
subjected to the effects of external
influence, the system moves in that direction
which tends to nullify the effects of the
external influence.
1. Calculate the equilibrium P
O2
over Ni at 1200
C. Determine the corresponding air pressure
below which NiO will begin to dissociate.

2. Calculate the equilibrium ratio P
H2
/P
H20
for the
oxidation of chromium in water vapor at 1000
C.

3. Characterize the relative thermal stability of
Si
3
N
4
and BN in a mixture of Si
3
N
4
and BN at 1
atm pressure. Assume all components are
pure. BN has been sugested as an abradable
high tem[erature coating. Si
3
N
4
is utilized in
high temperature ceramic applications.
Heterogeneous Condensed Phase
Dissociation of CO
2
2CO
2(g)

2CO
(g)
+

O
2(g)
Example:
1. Consider the following reaction in the roast reduction
reaction(2
nd
stage converster) at 1000K, in copper
smelting
2Cu
2
O
(l)
+Cu
2
S
(l)
6Cu
(l)
+SO
2(g)
Given the following data:
2Cu
(l)
+

O
2(g)


Cu
2
O
(l)
AG
T
=-40,500-3.92TlogT +29.5T

2Cu
(l)
+ S
2(g)


Cu
2
S
(l)
AG
T
=-30,610+6.80T
1/2 S
2(g)
+

O
2(g)

SO
2(g)
AG
T
=-86,620+ 17.31T

AG
1000K
=
2. Consider the Kroll process
TiO
2(s)
+2Cl
(g)
TiCl
4(g)
+O
2(g)
T=1000C
Determine the partial pressures of the product gases
before the reaction ceases to produce the
titanium chloride if the operation is done at 1atm
pressure.

Given:
Ti
(s)
+ 2Cl
2(g)


TiCl
4(g)
AG
T
= -180,700-1.8logT +34.65T

Ti
(s)
+ O
2(g)


TiO
2(g)
AG
T
= -2,184,600+ 41.74T
C
(s)
+ O
2(g)


CO
(g)
AG
T
= -26,700- 20.95T



Raoults Law
The vapor pressure exerted by a dissolved
component A, P
A
, in a homogeneous
condensed solution is equal to the product of
the atomic fraction of A in the solution, X
A
, and
the vapor pressure of pure A, P
A
, at the
temperature of the solution
P
A
= X
A
P
A
a
A
=X
A
Sixty moles of an ideal gas mixture at 5
atmosphere pressure contains 15 moles of
S
2(g)
in contact with microcrystalline quartz,
SiO
2(s)
. If analysis of the quartz reveals that it
contains no sulfur impurities, calculate the
activity of S
2(g).
(P
s2(g)
=1atm)