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Electrochemistry and Corrosion

Professor Brian Kinsella
Corrosion
• Corrosion can be defined as the deterioration
of a substance by reaction with its’
environment.
• Strictly speaking this definition includes non-
metals as well as metals, for example, plastics
and ceramics. However, for this course
corrosion will focus on the corrosion of metals
which is mainly by electrochemical reactions.
Assignment 1 – Corrosion of
Reinforcing Bar in Concrete
• Often referred to as concrete cancer – this area of
corrosion amounts to tremendous costs to
government, industry and society.
• It affects concrete structures of wharves, bridges, tall
buildings and pathways.
• The problem is caused by oxygen corrosion of the
mild steel reinforcing bar. The iron oxide corrosion
product occupies a larger volume then the iron and
this results in high internal pressure causing the
concrete to crack and spall (break in chips or flakes).
Assignment 1 – Corrosion of
Reinforcing Bar in Concrete
• Under normal circumstances the steel does not
corrode due to the high pH of concrete and the
formation of a passive (protective oxide) film which
can form under this condition.
• Destruction of the passive film can be attributed to
ingression of chloride ions and carbon dioxide.
• There are a number of techniques used to prevent
corrosion taking place, including cathodic protection.
• There are also a number of techniques used to treat
the problem once it has occurred.
• In your assignment you will need to cover the
corrosion mechanism, the methods of prevention
and the methods of treatment.
Assignment 1 – Corrosion of
Reinforcing Bar in Concrete
• Key topics to look for:
1. Pourbaix diagram
2. Cathodic protection methods
3. Inhibitors
4. Quality of concrete

• Comment on the effectiveness of prevention
and cure.
Basic Thermodynamics
• Gas Laws
Basic Thermodynamics – Gas Laws and Constant
( )( )
( )( )
( )( )
( )( )
( )( )
( )( )
1 - 1 -
3 2 - 5
1 - 1 - 7
3 2 - 6
1 - 1 -
mole deg joules 8.314
deg 16 273 mole 1
meter 0224136 0 meter newtons 10 013 1
mole deg ergs 10 8.314
deg 16 273 mole 1
cm 6 413 22 cm dyne 10 013 1
units second) - kilograms - (meter mks and cgs in R constant Gas
mole deg atm - l 0820549 0
deg 160 273 mole 1
l 4136 22 atm 1
=
×
= =
× =
×
= =
=
= =
=
.
. .
.
. , .
.
.
.
nT
PV
R
nT
PV
R
nT
PV
R
nRT PV
Gas Constant
• The calorie is equal to 4.1840 joules



• The equation is used to determine the number of
moles of a gas if P, V and T are known or P, V or T if
the other parameters are known.
• It is important to remember that 1 mole of gas will
occupy 22.4 liters at 1 atmosphere and 0
o
C.




( )
( )
1 - 1 -
1
-1 -1
mole deg cal 987 . 1
cal joules 184 . 4
mole deg joules 314 . 8
= =
÷
R
Gas Constant
• Note: The value of R = 8.314 joules deg
-1
mole
-1


is used in the Nernst Equation

( )
( )
( )( )( )
( )
( )
( )
r
p
r
p
a
a
n
E E
n
E E
a
a
nF
RT
E E
log
0591 . 0
500 , 96
1 . 298 314 . 8 303 . 2
ln
0
0
0
÷ =
÷ =
÷ =
Daltons Law – The total pressure of a gas in a
liquid is equal to the sum of the partial pressures
of the gases in the mixture
The total number of moles of a gas in a mixture is equal to
the sum of the numbers of moles of the different gases




Where lower case p is used to represent the partial
pressure




· · · + + + =
· · · + + + =
· · · + + + =
c b a
c b a total
c b a total
p p p
V
RT
n
V
RT
n
V
RT
n
V
RT
n
n n n n
total
P
Raoult’s Law
• The mole fraction of a component in the
vapor is equal to the pressure fraction in the
vapor
• E.g. for two components

components pure the of pressure partial the are
and and fractions mole the are and where
2
1 2 1
2 2 2
1 1 1




p
p X X
p X p
p X p
=
=
Raoult’s Law
 

2 2 1 1
1 1
2 1
1
, 1
p X p X
p X
p p
p
X
vap
+
=
+
=
Raoult’s Law – Ideal Solutions
• Example: The vapor pressure of benzene and toluene at 60
o
are 385 and 139 mm. Calculate the partial pressure of
benzene and toluene, the total vapor pressure of the solution,
the mole fraction of toluene in the vapor above a solution
with 0.60 mole fraction toluene.
• p
benzene
= 0.4 x 385 = 154
• p
toluene
= 0.6 x 139 = 83.4
• P
total
= 237.4

351 0
4 237
4 83
vap toluene
.
.
.
= = X
Note that the more
volatile component is
more concentrated in the
vapor. In this case
benzene is more volatile
and the mole fraction of
benzene in the vapor will
be 154/237.4 = 0.649
Raoult’s Law – Ideal Solutions
• The law enables the determination of volatile
components such as pentane and hexane in the gas
phase for top of the line corrosion mechanisms.
• The law predicts that the vapor pressure of a pure
component will decrease due to the presence of a
non volatile soluble material, e.g. salt in water will
decrease the mole fraction of water and its vapor
pressure.
• Does the corrosivity of CO
2
gas decrease under super
saline conditions?
Henry's Law - Non Ideal Solutions
• For dilute solutions, the partial pressure of the
component present at lower concentration is
directly proportional to its mole X
2






• For ideal solutions K
2
= p
2
o
and Henry’s law
becomes identical to Raoult’s law

constant law s Henry'
(solute) conc. low at component the is where
2
2
2 2 2
=
=
K
X
K X p
Henry's Law - Non Ideal Solutions
Gas K
2
Water 25
o
C
H
2
5.34 x 10
7

N
2
6.51 x 10
7
O
2
3.30 x 10
7
CO 4.34 x 10
7

CO
2
1.25 x 10
6

CH
4
31.4 x 10
6

C
2
H
6
23.0 x 10
6
K
2
= P
2
/X
2
The partial pressure of
the gas is in mm and the conc.
units are mole fraction
Henry's Law - Non Ideal Solutions
• Calculate the solubility of CO
2
in water at 25
o
C at a CO
2
pp of
760 mm

1 - 2
6
2
2
6
2
2
liter mole 10 38 . 3
10 25 . 1
55 . 55 760
1000/18.02 O H of moles of number the to
compared negligible is and g 1000 mL 1000 assume
solution of
litre per CO of moles of number the is where
02 . 18
1000 760
10 25 . 1
2
2
2
2
2
÷
× =
×
×
=
=
=
|
.
|

\
|
+ = ×
=
CO
CO
CO
CO
CO
n
n
n
n
n
X
p
K
Henry's Law - Non Ideal Solutions
• X
2
= moles CO
2
/moles CO
2
+ moles H
2
O
• X
2
= moles CO
2
/moles CO
2
+ 1000/18 H
2
O
• X
2
= moles CO
2
/moles CO
2
+ 55.556 H
2
O
• X
2
~ moles CO
2
/55.556 H
2
O
• 1/X
2
~ 55.556/moles CO
2
• ~55.556 n
CO2






Consequence of Dalton’s Raoult’s and Henry’s Law
• It is important to remember Dalton’s, Raoult’s and
Henry’s laws when preparing corrosive gas mixtures.
• E.g., If you need to determine the corrosive effect of
1 ppm dissolved oxygen. Knowing that seawater
contains about 10 ppm dissolved oxygen at 20
o
C and
1 bar (760 mm), i.e., 80% N
2
and 20% O
2
. A gas
mixture of 98% N
2
and 2% O
2
should result in 1 ppm
dissolved oxygen.
• The same result can be obtained by bubbling
nitrogen and oxygen into your test solution at the
rates of 98 and 2 mL s
-1
respectively (or 196 and 4 mL
minute
-1
,

respectively – etc).
Consequence of Dalton’s Raoult’s and Henry’s Law
• Alternatively, to study the corrosivity of CO
2
at 0.2
bar, you can achieve the required concentration by
bubbling N
2
and CO
2
gas into your test solution at 20
and 80 mL minutes
-1
respectively.
• You are required to compare the corrosivity of acetic
acid with CO
2
at 0.2 bar to steel. Determine the
molar concentration of acetic acid required since for
comparison, both acids need to be at the same molar
concentration.
• CO
2
+ H
2
O

↔ H
2
CO
3

First Law of Thermodynamics
• 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.

Reversible Expansion of a Gas
2 1 1 2
2
1
1
2
2
1
2
1
2
1
since
P
P
log 303 2
V
V
log 303 2
P P V V
nRT nRT w
V
dV
nRT dV
V
nRT
PdV w
w q dE
w q E
rev
v
v
v
v
v
v
rev
=
= =
= = =
÷ =
÷ = A
} } }
. .
o o
The work performed during the expansion of a gas
can be related to changes in pressure or volume.
Dependence of Internal Energy on Temperature
and Volume
V V
V
V
V
T V
T V
T
E
T
q
C
C
dT q
dT
T
E
q
dV
V
E
P dT
T
E
d
PdV q dE
dV
V
E
dT
T
E
dE
|
.
|

\
|
c
c
= |
.
|

\
|
c
=
|
.
|

\
|
c
c
=
(
¸
(

¸

|
.
|

\
|
c
c
+ +
|
.
|

\
|
c
c
=
÷ =
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
o
o
o
o
o
volume. constant at system the of
capacity heat the as known is and volume constant at
ally experiment measured be may quantity the

constant held is system the of volume the if
Energy
• For an ideal gas:

}
=
=
|
.
|

\
|
=
+ =
2
1
2 1
is to from heated gas of
mole a for energy internal in change The
T
T
V
V
V
V
dT C
T T
dT C dT
T
E
dE
PdV dT C q
ΔE


o
Enthalpy
• Constant pressure process

( )
( ) ( )
dp
P
H
dT
T
H
dH
H q
PV E H
PV E PV E q
V V P q E E
V P q E
T P
|
.
|

\
|
+
|
.
|

\
|
=
A =
+ =
= + + =
=
A ÷ = A




enthalpy function state New
adsorbed heat the -
- - -
1 1 2 2
1 2 1 2
Constant pressure and Relationship between C
P
and
C
V



• The ratio is the heat capacity at constant pressure, C
p




dT
T
H
q
p
p
|
.
|

\
|
c
c
= o
dT q
P
c
R C C
C C
dP
T
H
dT C dH
T
H
dT
q
C
V P
V P
P
p
P
p
p
= ÷
|
.
|

\
|
c
c
+ =
|
.
|

\
|
c
c
=
c
=
pressure constant at
heated i s substance a when done i s work vol ume
pressure because than l arger al ways i s
Reversible Adiabatic Expansion of a Gas
1
2
1
2
V
V
R
T
T
C
V
dV
R
T
dT
C
V
V
ln ln ÷ =
÷ =
No loss or gain of heat to the environment –
the system is thermally isolated so that q = 0
Reversible Adiabatic Expansion of a Gas
• Calculate the temperature increase and final pressure of He if
a mole is compressed adiabatically and reversibly from 44.8
liters at 0
o
C to 22.4 liters. The molar heat capacity of He = 3.00
cal deg
-1
mole
-1
. R must be expressed in the same units.




( ) ( )
( ) ( )
( )( )
o
o
V
K T
T
T
V V R T T C
159.3 e temperatur in Increase
4 432
1 273 2 1 00 3 987 1
8 44 4 22 303 2 987 1 1 273 303 2 0 3
2
2
2
1 2 1 2
=
=
+ ÷ =
× ÷ = ×
÷ =
.
. log log . / . log
. . log . . . log . .
ln ln
Molar Heat Capacity of Gases cal deg
-1
mole
-1
at 25
o
C


Gas C
p
C
v
C
p
/ C
v

Argon 4.97 2.98 1.67
Helium 4.97 2.98 1.67
Hydrogen 6.90 4.91 1.41
Oxygen 7.05 5.05 1.40
Nitrogen 6.94 4.95 1.40
Carbon Dioxide 8.96 6.92 1.29
Methane 8.60 6.59 1.31
Ethane 12.71 10.65 1.19
Heat Capacity of Solids
• Debye showed that at sufficiently low
temperature


• The quantity u, the characteristic temperature
of a substance, is usually of the order of 100-
400
o
K. The equation is suitable for
extrapolating heat capacity data below 15
o
K

3
4
5
12
|
.
|

\
|
=
u
t
T
R C
V
Standard State
• The change in enthalpy ΔH or internal energy ΔE for a
reaction depends on the states of the reactants and
products. E.g. the heat of combustion of graphite is
different from that of diamond. To facilitate the
tabulation of thermodynamic data certain standard state
are adopted and thermodynamic properties are
tabulated to these standard states. The standard state of
a gas is the ideal gas at 1 atm at the temperature
concerned; for a liquid it is the pure liquid at 1 atm at the
temperature concerned; for a solid it is a specified
crystalline state at 1 atm at the temperature concerned.
The standard form of carbon is graphite and the standard
form of sulfur is rhombic sulfur. In writing equations,
solids, liquids, and gases are designated by (s), (l), and (g)
respectively, since the enthalpy change depends on the
physical state of the reactants and products. The
standard state refers to temperature at 25
o
C unless
otherwise specified.
Calculation of the Heat of a Reaction at Constant Pressure, from
the Heat of Reaction at Constant Volume



The standard heat of combustion of n-heptane at constant volume and
25
o
C is 1148.93 kcal
C
7
H
16
(l) + 11O
2
(g) = 7CO
2
(g) + 8 H
2
O(l)
ΔE
o
= -1,148.93 kcal mole
-1

Estimate the heat absorbed at constant pressure
q
p
= q
v
+ RTΔn = -1,148,930 – (1.987)(298.1)(4)
= 1,151,300 cal mole
-1
or

1,151.30 kcal mole
-1

( ) ( )
( ) ( )
n RT q q
n RT E H
V P E H
V P
P p
P p
A + =
A + A = A
A + A = A
Application of First Law to Thermodynamics
• Calc. of ∆H when carbon burns to carbon monoxide
• It is difficult to burn C only to CO
( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) kcal 4157 . 26 s C
kcal 6361 . 67
kcal 0518 . 94 s C
kcal 6361 . 67
kcal 0518 . 94 ) ( ) (
2 2
1
2 2
1
2
2 2
2 2 2
1
2 2
÷ = A = +
= A + =
÷ = A = +
÷ = A = +
÷ = A = +
H g CO g O
H g O g CO g CO
H g CO g O
H g CO g O g CO
H g CO g O s C
Note the change in polarity
for the reverse reaction
Enthalpy of Formation
• Standard enthalpy change for a reaction is equal to the sum of
the enthalpies of the products minus the sum of the
enthalpies of the reactants at the temperature concerned.


• v
i
and v
j
are the stochiometric coefficients in the balanced
chemical equations for reactants and products, respectively.
• The molar enthalpy for each element in its standard state is
given the value zero.
¿ ¿
÷ = A
0 0
0
react
i
prod
j
H v H v H
Enthalpy of Formation
• For example the enthalpy of formation of CO
2
is the enthalpy
change for the following reaction.




• Since the enthalpy of combustion of hydrogen to form liquid
water at 298
o
K is –68,317.4 cal mole
-1
, the enthalpy of
formation of H
2
O(l) is –68,317.4 cal mole
-1
. The enthalpy of
formation of gaseous water is less negative by the molar heat
of vaporisation of water at 25
o
C, which is 10,519.5 cal mole
-1
.
Therefore the enthalpy of formation of H
2
O(g) @ 25
o
C is
-57,797.9 cal mole
-1


( ) ( ) ( )
1 -
298 ,
-1
2 2
mole cal 8 . 051 , 94 so and
mole cal 8 . 051 , 94 H
÷ = A
÷ = A = +
o
f
o
o
H
g CO g O graphite C
Enthalpy of Formation
• When a substance cannot be formed directly in a
rapid reaction from its elements, the enthalpy
change for a series of suitable reactions may be
utilized in calculating the enthalpy of formation.
• Example: calculate the enthalpy change of H
2
SO
4
(l)
from the enthalpy change for the combustion of
sulfur to SO
2
, the oxidation of SO
2
to SO
3
using a
platinum catalyst, and the heat of solution of SO
3
in
water to give H
2
SO
4
at 25
o
C
Enthalpy of Formation
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) ( ) kcal 193.91 - 2
kcal -68.32
kcal -31.14
kcal -23.49
kcal -70.96
0
4 2 2 2
0
2 2 2
1
2
0
4 2 2 3
0
3 2 2
1
2
0
2 2
= A = + +
= = +
= = +
= = +
= = +
f H l SO H g H g O s S
ΔH l O H g O g H
ΔH l SO H l O H g SO
ΔH g SO g O g SO
ΔH g SO g O s S
Enthalpy of Formation
• Consider the following

( ) ( )
0
2
1
0 0
0
2
1
0 0 0 0 0
0
,
0
,
0
2 2 2
1
2 2
2 2 2
2



O CO CO
O C CO O C CO
CO f CO f
H H H
H H H H H H
H H H
CO O CO
÷ ÷ =
÷ ÷ ÷ ÷ ÷ =
A ÷ A = A
= +
Enthalpy of Formation
• The enthalpy of formation of many compounds, ions,
and atoms are accurately know. From these
enthalpies of formation the enthalpy change for
many reactions may be calculated by use of the
equation given.
• The standard state of a solute in aqueous solution is
taken as the hypothetical ideal state of unit molality,
in which the enthalpy of the solute is the same as in
the infinitely dilute solution.

Enthalpy of Formation



Enthalpy of formations at 25
o
C, elements and
inorganic compounds in kcal mole
-1

H
2
O(l) -68.3174 CO
2
(g) -94.0158
H
2
O(g) -57.7979 H
2
S(g) -4.815
Br
2
(g) 7.34 HCl(g) -22.063
Fe
2
O
3
(s) -196.5 Fe
3
O
4
(s) -267.0
S
(monoclinic
0.071
C(s,
diamond)
0.4532
Enthalpy of Formation
Enthalpy of formations at 25
o
C, in kcal mole
-1
, organic
compounds
Methane,
CH
4
(g)
-17.889 Ethane C
2
H
6
(g) -20.236
Benzene,
C
6
H
6
(g)
19.820
Benzene,
C
6
H
6
(l)
11.718
Acetic acid,
CH
3
COOH(l)
-116.4
Formic acid,
HCOOH(l)
-97.8
Oxalic acid,
(COOH)
2
(s)
-197.6
Acetylene,
C
2
H
2
(g)
54.194
Enthalpy of Formation
Enthalpy of formations at 25
o
C, in kcal mole
-1
, Ions in Water
H
+
0.000 OH
-
-54.957
Cl
-
-40.023 ClO
4
-
-31.41
CO
3
2-
-161.63 NO
3
-
-49.372
SO
4
2-
-216.90 PO
4
3-
-306.9
S
2-
10.0 HS
-
-4.22
Na
+
-57.279 Ca
2+
-129.77
Enthalpy of Formation
Enthalpy of formations at 25
o
C, in kcal mole
-1
, Solutes and Solution
NaOH(s)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-101.99
-112.108
-112.1
-112.236
NaCl(s)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-98.232
-97.250
-97.216
-97.302
NaAc(s)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-169.8
-173.827
-173.890
-174.122
HAc(l)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-116.4
-116.705
-116.724
-116.743
HCl(g)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-22.063
-39.731
-39.798
-40.023
NaNO
3
(s)
in 100 H
2
O
in 200 H
2
O
in ∞ H
2
O
-111.54
-106.83
-106.73
-106.651
Heat
absorbed
solution
becomes
colder
Heat
evolved
solution
heats up
Heat of Solutions
• Substance dissolving in water
• Calculate the integral heat of solution of 1 mole of HCl(g) in
200H
2
O(l)
• The reaction involves HCl gas dissolving in two hundred moles
of water to produce a solution of HCl (1 mole in 200 moles of
water)

( ) ( )
( )
( )
kcal 35 17
063 22 798 39
200 in 200
0

0
2
200 in
0
298
2 2
.
. .
H H H
O H HCl l O H g HCl
g HCl f O H HCl f
÷ =
÷ ÷ ÷ =
A ÷ A = A
= +
, ,
Heat of Dilution
• Calculate the integral heat of dilution for the addition
of 195 moles of water to 1 mole of HCl in 5 moles of
water. The enthalpy of formation of HCl in 5 moles of
H
2
O is -37.37 kcal and the enthalpy of formation in
200 moles of water is -39.798 kcal.

( )
( )
kcal 43 . 2
37 . 37 798 39
200 in 195 5 in
0
5
0
200
0
298
2 2 2
2 2

.
H H H
O H HCl l O H O H HCl
O H f, HCl in O H f, HCl in
÷ =
÷ ÷ ÷ =
A ÷ A = A
= +
Enthalpies of Formation of Ions
• Since for strong electrolytes in dilute solution the
thermal properties of the ions are essentially
independent of the accompanying ions, it is
convenient to use relative enthalpies of formation of
individual ions. The sum of the enthalpies of
formation of H
+
and OH
-
ions may be calculated.


( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) ( ) kcal 957 . 54
kcal 317 . 68
kcal 360 . 13
0
2 2
1
2
0
2 2 2
1
2
0
2
÷ = A + = +
÷ = A = +
= A + =
÷ +
÷ +
H aq OH aq H g O g H
H l O H g O g H
H aq OH aq H l O H
Enthalpies of Formation of Ions
• The separate enthalpies of formation of H
+
and OH
-

cannot be calculated, but if the enthalpy of
formation of H
+
(aq) is arbitrarily assigned the value
zero, it is possible to calculate relative enthalpies of
formation for other ions. Denoting the electron by e,
the convention is that.


• Therefore the enthalpy of formation of OH
-
is given
by

( ) 0 ) (
0
2 2
1
= + = +
+
ΔH e aq H aq g H
( ) ( ) ( ) kcal 957 . 54
0
2 2
1
2 2
1
÷ = A = + + +
÷
H aq OH e aq g O g H
Enthalpies of Formation of Ions
( ) ( ) ( ) ( )
( ) ( ) kcal 023 . 40
kcal 023 . 40
0
2 2
1
0
2 2
1
2 2
1
÷ = A = +
÷ = A + = + +
÷
÷ +
f
H aq Cl aq g Cl
H aq Cl aq H aq g Cl g H
Bond Energies
• The bond energy E(A-B) is the contribution of the bond between a
particular pair of atoms A-B in a molecule to the total binding
energy of the molecule. The total binding energy is required to
dissociate the molecule into atoms, each in its ground state. Bond
energies are usually given for a reference temperature of 298
o
C.
• For a diatomic molecule the bond energy is the heat of dissociation
of the molecule.
• In molecule of the type, A-B
n
where all n bonds are identical, the
bond energy of the A-B bond is 1/n times the heat of dissociation of
into A + nB.
• For polyatomic molecules having several types of bonds, it is not
possible to make precise assignment of bond energies, but in a
series of similar compounds bond energies for different bonds may
be assigned in such a way as to reproduce as much as possible the
heat of atomization of all compounds in the series.
Bond Energies






• E(C-H) = 394/4 = 98 kcal. This may be compared with the energy of
dissociation of successive hydrogen atoms of methane.


( ) ( ) ( )
( ) ( )
( ) ( )
( ) ( ) ( ) kcal 394 4
kcal 170
kcal 206 4 2
kcal 18 2
0
4
0
0
2
0
2 4
= A + =
= A =
= A =
= A + =
H g H g C g CH
H g C graphite C
H g H g H
H g H graphite C g CH
Bond Energies





• These bond-dissociation energies are all different because of the different
structure of the parent molecules. The sum of the four bond-dissociation
energies is equal to four times the bond energy.


• Since the initial and final states are the same in the two cases.
• The bond dissociation energies D are known only for a few polyatomic
molecules. When they are known they are more useful in kinetic and
other calculations than the bond energies calculated from thermodynamic
data.

( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) kcal 81
kcal 125
kcal 87
kcal 103
2
2 2 3
3 3 4
= ÷ + =
= ÷ + =
= ÷ + =
= ÷ + =
H C D g H g C g CH
H CH D g H g CH g CH
H CH D g H g CH g CH
H CH D g H g CH g CH
( ) ( ) ( ) ( ) ( ) H C E H C D H CH D H CH D H CH D ÷ = ÷ + ÷ + ÷ + ÷ 4
2 3
Bond Energies
Bond Energies E(A-B) (in kcal mole
-1
)
C÷C 80.5 O÷O 34
C=C 145 O÷H 109.4
C≡ C
198 H÷H 103.2
C÷H 98.2 N÷N 37
C÷Cl 78 N÷H 92.2
C÷O 79 Cl÷Cl 57.1
Bond Energies
• The heat of a reaction may be estimated by adding the bond
energies for the bonds that are broken and subtracting from
this total the bond energies for the new bonds formed in the
reaction.
• C
2
H
4
+ H
2
= C
2
H
6

• H÷H bond is broken ∆H
o
= 103.2 kcal
• C=C bond is broken ∆H
o
= 145 kcal
• C÷C bond is formed ∆H
o
= -80.5 kcal
• 2(C÷H) bonds are formed ∆H
o
= -196.4 kcal
∆H
o
= -29 kcal

• Compared with experimental value of 32.73 kcal mole
-1


Heat Adsorbed in Heating a Gas
• Molar heat capacity of gases at constant pressure (in cal deg
-1

mole
-1



2
cT bT a C
p
+ + =
Gas a b x 10
3
C x 10
7

H
2
6.9469 -0.1999 4.808
N
2
6.4492 1.4125 -0.807
O
2
6.0954 3.2533 -10.171
CO
2
6.3957 10.1933 -35.333
H
2
O 7.1873 2.3733 2.084
NH
3
6.189 7.887 -7.28
CH
4
3.422 17.845 -41.65
Heat
Capacity is a
function of
temperature
Heat Absorbed in Heating a Gas
• The molar heat capacities of simple gases can be
calculated on the basis of spectroscopic data more
accurately than can be determined directly,
especially at high temperature.
• To calculate the heat adsorbed per mole at constant
pressure when the temperature of a substance is
raised, the equation dH = C
p
dT

( )
( ) ( ) ( )
3
1
3
2 3
2
1
2
2 2 1 2
2
2
1
2
1
1
2
T T T T T T a
dT cT bT a dT C H H H
c b
T
T
T
T
P
T
T
÷ + ÷ + ÷ =
+ + = = ÷ = A
} }
Heat Absorbed in Heating a Gas
• When the temperature change is small or the
variation of the heat capacity with temperature is
small, it is satisfactory to use the average heat
capacity in this temperature range.

( )
1 2
avg
T T C H
p
÷ = A
Dependence of the Heat of Reaction on
Temperature
• If we know the enthalpy of reaction at temperature
T
1
we can calculate the temperature of reaction at
temperature T
2
, provided the heat capacities of A
and B are known







• The enthalpy change of reaction T
2
is equal to the
sum of three terms.

dT C
T
T
A P
}
1
2
,
}
2
1
,
T
T
B P
dT C
A B
A B
∆H
2

T
2

∆H
1

T
1

Dependence of the Heat of Reaction on
Temperature



• Since the enthalpy change is independent of the path
chosen between two states. It is convenient to write
this equation

} }
+ A + = A
2
1
1
2
,
1
,
2
T
T
B P
T
T
A P
dT C H dT C H
A P B P P
T
T
P
C C C
dT C H H
, ,
1 2
Δ where
2
1
÷ =
A + A = A
}
Dependence of the Heat of Reaction on
Temperature
• If the heat capacities of reactant and product are independent
of temperature between T
1
and T
2
, may be placed in
front of the integration sign and


• Calculate the heat evolved in the freezing of water at constant
pressure and a temperature to -10
o
C.
• H
2
O(l) = H
2
O(s)
• Given ∆H
273
=-79.7 cal g
-1
, C
p,H2O.l
= 1.00 cal deg
-1
g
-1
, C
p,H2O,S
=
0.49 cal deg
-1
g
-1
P
C A
( )
1 2 1 2
T T C H H
P
÷ A + A = A
Dependence of the Heat of Reaction on
Temperature
( ) ( )
| |( )
| |( )
( )( )
1 -
273 263
273 263
2 2
273 263
g cal 6 74 1 5 7 79

10 51 0
10 0 1 49 0
273 263
. . .
.
. .
, ,
÷ = + ÷ =
÷ ÷ + A = A
÷ ÷ + A = A
÷ ÷ + A = A
H H
H H
C C H H
l O H P s O H P
General Treatment of the Effect of Temperature on the
Enthalpy of Reaction
• For a general chemical reaction
• aA + bB = cC + dD
• the enthalpy change is
• The rate of change of ∆H with temperature is obtained by
differentiating with respect to temperature at constant pressure


B A D C H b H a H d H c H ÷ ÷ + = A
( )
( )
( )
P
B P A P D P C P
P
P
P
P
B
P
A
P
D
P
C
P
C C b C a C d C c
dT
H d
C dT H d
dT
H d
b
dT
H d
a
dT
H d
d
dT
H d
c
dT
H d
A = ÷ ÷ + =
(
¸
(

¸

A
=
|
|
.
|

\
|
÷
|
|
.
|

\
|
÷
|
|
.
|

\
|
+
|
|
.
|

\
|
=
(
¸
(

¸

A
, , , ,
that see we , that g Rememberin
General Treatment of the Effect of Temperature
on the Enthalpy of Reaction
• The previous equation may be stated in words as follows: the
change in enthalpy of reaction at constant pressure per
degree rise in temperature is equal to the change in heat
capacity at constant pressure of the system as the result of
the reaction.
• The equation may be integrated between two temperatures
T
1
and T
2
to obtain the relation between the enthalpy changes
at these two temperatures.

( )
} }
A = A ÷ A = A
A
A
2
1
1 2
2
1

T
T
P
H
H
dT C H H H d
General Treatment of the Effect of Temperature
on the Enthalpy of Reaction
• By use of this equation it is possible to calculate ∆H for a
reaction at another temperature if it is known at one
temperature and if the values of C
P
are known in the
intervening temperature range. The empirical equations for
expressing as a function of temperature are very good for
this purpose.
• Calculate the heat of combustion of hydrogen at 1500
o
K

P
C
Heat Capacity of Gases
@ Const. P in cal deg
-1
mole
-1

Gas a b x 10
3
c x 10
7

H
2
6.9469 -0.1999 4.808
O
2
6.0954 3.2533 -10.171
CO
2
6.3957 10.1933 -35.333
H
2
O 7.1873 2.3733 2.084
NH
3
6.189 7.877 -7.28
CH
4
3.422 17.845 -138.27
C
2
H
6
1.375 41.852 -225.82
2
CT bT a C
P
+ + =
General Treatment of the Effect of Temperature
on the Enthalpy of Reaction
( ) ( ) ( )
( )
( )
767 , 119
10 723 . 4 10 8931 . 1 6146 . 5 8 . 598 , 115
obtain to 2 2
: equation
following the into d substitute are tables from capacities heat molar The
cal 8 . 598 , 115 H 2 2
0
1500
1500
298
2 7 3 0
1500
1500
298
, , ,
0
298
0
1500
o
298 2 2 2
2 2 2
=
× + × + ÷ + ÷ =
÷ ÷ + =
÷ = A = +
}
}
÷ ÷
ΔH
dT T T ΔH
dT C C C ΔH ΔH
g O H g O g H
O P O P O H P
The equation is only applicable if there is no change in
phase in going from T
1
to T
2.