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# CM 1502 1

## The First Law of Thermodynamics

1. Introduction to Thermodynamics
2. The First Law of Thermodynamics
3. Systems, Surroundings and the Boundary
4. Internal Energy
5. Types of Systems
6. State Functions
7. Heat Enthalpy, Heat Capacities and Calorimetry
8. Work Reversible, Irreversible and Adiabatic Paths
9. Enthalpy Hesss and Kirchhoffs Law
CM 1502 2
Introduction to Thermodynamics
Thermo = Heat Dynamics = Movement
Inter-conversion: Heat Work
So generally, heat and/or work are referred to as energy.

- movement/transfer and
- inter-conversion/transformation, of energy.

The science that describes what is possible and what is
impossible during energy transfer and transformation
processes.

CM 1502 3
The Laws of Thermodynamics
There are two fundamental laws of thermodynamics, first
and second. The zeroth and third laws are more specific.

Zeroth: If two thermodynamic systems are in thermal
equilibrium with a third, they are also in thermal
equilibrium with each other.

Third: As a system approaches absolute zero
temperature (0 K), all processes cease and the entropy
(disorder) of the system approaches a minimum value
(zero).

*
CM 1502 4

First Law of Thermodynamics

Identical to the principle of conservation of energy.
- energy cannot be created nor destroyed.
- energy can be only be transferred; or transformed
from one form to another.

The total energy in the universe is constant.

CM 1502 5
Transfer of Energy
Must define origin of transfer and the destination of transfer.
So we define two parts the system and the surroundings.

System: the specific part of the universe on which we choose to
focus. It usually consists of a definite amount of specific substance
with its own internal energy (U).

Surroundings: everything else in the universe, but we need to
consider only the part that interacts with the system.

A system may be separated from it surroundings by a boundary
through which matter and energy may exchange between them.

CM 1502 6
Figure 6.1
the system
the surroundings
CM 1502 7
E
universe
= E
system
+ E
surroundings

Units of Energy
Joule (J)
Calorie (cal)
British Thermal Unit (Btu)
1 cal = 4.18 J
1 J = 1 kg*m
2
/s
2

1 Btu = 1055 J
= 0
First law of thermodynamics
change in
+E
system
= -E
surroundings
-E
system
= +E
surroundings
or
CM 1502 8
E = E
final
- E
initial
= E
products
- E
reactants

Energy diagrams for the transfer of energy
between a system and its surroundings.
U = Internal energy of the system
I
n
t
e
r
n
a
l

E
n
e
r
g
y
,

U

I
n
t
e
r
n
a
l

E
n
e
r
g
y
,

U

CM 1502 9
Figure 6.3
Energy diagrams for the transfer of heat only
between a system and its surroundings.
I
n
t
e
r
n
a
l

E
n
e
r
g
y
,

U

I
n
t
e
r
n
a
l

E
n
e
r
g
y
,

U

q = heat
CM 1502 10
Figure 6.4
Energy, E
Zn(s) + 2HCl(aq)
ZnCl
2
(aq) + H
2
(g)
E<0
work done on
surroundings
w < 0
Energy diagrams for the transfer of work only
from the system to its surroundings.
Internal Energy, U
w = work
*
CM 1502 11
U = q + w
Positive convention is taken when
the direction is into the system.
Negative convention is taken when
the direction is out of the system.
For q:
+ means system gains heat U ;
- means system loses heat U .
For w:
+ means work done on system
compression U ;
- means work done by system
expansion U .
q
w
CM 1502 12
An electric battery is charged by supplying 290 kJ of electrical work, but
in the process it loses 45 kJ as heat to its surroundings. What is the
change in internal E of the battery?

w = +290 kJ q = -45 kJ

U = q + w = (-45 kJ ) + (+290 kJ ) = +245 kJ
CM 1502 13
Internal Energy (U):
the combined kinetic and potential
energies of all the particles in a system.
*
At a molecular level,
potential energy is:
At a molecular level,
kinetic energy is:
CM 1502 14
The Piston
The piston as the chosen system.
q: + means system gains heat.
w: + means work done on system
P
ext
> P
gas
compression.
w: - means work done by system
P
ext
< P
gas
expansion.
q: - means system loses heat.
CM 1502 15
Types of Systems
Isolated system
No exchange of matter, q or w

No exchange of matter and q
Can exchange w across boundary

Closed system
No exchange of matter
Can exchange q and w across boundary

Open system
Can exchange matter, q and w with
its surroundings

CM 1502 16
Type of Systems
Matter X X X
q X X
w X
*
Fill in the boxes with X for no exchange and for exchange.
CM 1502 17
State Functions
State functions of a system have the following characteristics:

(i) the value of a state function of a system depends only on
the current state of the system;

(ii) is independent of the path by which the state was reached;

(iii) and so state function =
final states (products) initial state (reactants).
CM 1502 18
Figure 6.6
CM 1502 19
Which are State Functions?
Pressure (P)
Volume (V)
Number of moles (n)
Temperature (T)
Internal energy (U)
Heat (q)
Work (w)

CM 1502 20
Heat and Work
q and w are not state functions because they do not
describe the state of a system.
e.g. what is the work of the system?

They are involved during a process when the system
changes states.

Their values depend on the path of the process.

U = q + w = U
f
- U
i
, U is a state function.
Non-state functions can contribute to state functions.
*
CM 1502 21
Measuring Heat
If you heat an object, T will increase. So, q T or q = constant x T

The constant is heat capacity the amount of q required to raise the T by
1 K, [units = J K
-1
].

But depends on how much substance is heated?

Specific heat capacity (c or s) the amount of q required to raise the T of
1 g of the substance by 1 K, [units = J g
-1
K
-1
]

Molar heat capacity (C) the amount of q required to raise the T of
1 mole of the substance by 1 K, [units = J mol
-1
K
-1
]

q = c x mass x T or q = C x n x T

For H
2
O, c = 4.184 J g
-1
K
-1
or C = 75.3 J mol
-1
K
-1
at 298 K. Mr (H
2
O) =
18 gmol
-1
, so 1 mole of H
2
O is 18 g.
CM 1502 22
What is the amount of heat necessary to raise the temperature of 8.5
kg of water from 12.5C to 84C?
q = c x mass x T
= 4.184 J g
-1
K
-1
x 8500 g x (84 12.5)C
= 2.5 x 10
6
J
CM 1502 23
Heat transfer under Constant V => U
If the system undergoes a process under constant V (isochoric),

U = q + w = q
V
+ 0 = q
V
U = q
V

How to measure q at constant volume (q
v
) i.e. U?

Constant volume bomb calorimeter
(calor is Latin for heat)

subscript is the constant property
CM 1502 24
Figure 6.10
A bomb calorimeter
COMBUSTION
CM 1502 25
Using a Bomb Calorimeter
Steps:

1. No substance.
q supplied to system (kJ ) = current x potential x time [1J = 1 AVs]
2. Measure rise in T or T
1
(C).
3. Calculate heat capacity of calorimeter (C
V
) = q/T
1

i.e. the amount of q required to raise the entire calorimeter T by 1 K
[units = kJ K
-1
].

4. Carry out reaction with substance.
5. Measure rise in T or T
2
(C).
6. q
V
= U = C
V
x T
2

CM 1502 26
http://www.ika.net/
most males: 1500 4000 kcal
most females: 900 2500 kcal
http://www.mcdonalds.com.sg/eatsmart_nutriinfo.html
CM 1502 27
A manufacturer claims that its new dietetic dessert has fewer than 30
kcal per serving. To test the claim, a chemist at the Department of
Consumer Affairs places one serving in a bomb calorimeter and burns it
in O
2
(the heat capacity of the calorimeter = 4.151 kJ K
-1
). The
temperature increases 59.35
0
C. Is the manufacturers claim correct?
The manufacturers claim is false.
q
V
= C
V
x T
= 4.151 kJ K
-1
x 59.35 K
= 246.36 kJ
= 246.36 kJ /4.18 J (1 cal = 4.18 J )
= 58.94 kcal
CM 1502 28
Heat transfer under Constant P => H
Enthalpy (H) is defined as H = U + PV = U + nRT ,
where H is also a state function.

If the system undergoes a process under constant P (isobaric),
H = U + PV
= q
P
+ w
P
+ PV (U = q + w)
= q
P
PV + PV (w = PV, see later)
H = q
P

How to measure q at constant pressure (q
P
) i.e. H?

Constant pressure coffee-cup calorimeter
CM 1502 29
Figure 6.9
Coffee-cup calorimeter
SOLID IN WATER

or

TWO REACTANTS REACT
IN WATER
H = q
P
= c
P
x mass x T (or = C
P
x n x T)

Heat transferred to water, so -q
solid/reactants
= q
water
-(c
solid/reactants
x mass
solid/reactants
x T
solid/reactants
) = (c
water
x mass
water
x T
water
)

and c
water
and mass
water
in the calorimeter are known and T
water
is measured.

CM 1502 30
P-V Diagrams for Heat Transfer under
Constant V and Constant P
lorien.ncl.ac.uk/.../Therm1/revers/isobar.htm
constant V constant P
U = q
v
H = q
p
CM 1502 31
Relationship
between C
v
and C
p
C
P
= q
P
/n T = H/n T
*
q
v
= C
v
n T = U
q
p
= C
p
n T = H
C
V
= q
V
/n T = U/n T
q = C x n x T

For 1 mol, C
p
C
v
= R
C
v
< C
p
by 8.314
For H
2
O, C
p
= 75.3 J mol
-1
K
-1
; C
v
= 67.0 J mol
-1
K
-1
T n
(PV)
C C
T n
U - (PV) U
C C
T n
U
T n
H
C C
v p
v p
v p

=

+
=

=
R C C Hence,
T n
(PV)
R
T nR (PV)
nRT PV
: reaction - non i.e. n, constant for
and law gas Ideal
v p
=

=
=
=
CM 1502 32
The First Law of Thermodynamics
1. Introduction to Thermodynamics
2. The First Law of Thermodynamics
3. Systems, Surroundings and the Boundary
4. Internal Energy
5. Types of Systems
6. State Functions
7. Heat Enthalpy, Heat Capacities and Calorimetry
8. Work Reversible, Irreversible and Adiabatic Paths
9. Enthalpy Hesss and Kirchhoffs Law
CM 1502 33
Measuring Work

Figure 6.7
Work involves a change in volume
against an opposing pressure.

w: - means work done by system
P
ext
< P
sys
expansion.

w: + means work done on system
P
ext
> P
sys
compression.

In most processes of interest to the
chemist, we have a reaction in the
system which causes an expansion.
w = P V
2
External (= system)
Why is w -ve for expansion?

w = -P(V
f
V
i
),
V
f
> V
i
, so w remains -ve.
after the
process
CM 1502 34
Why is w +ve for compression?

w = -P(V
f
V
i
),
V
f
< V
i
, so V is -ve, hence w is +ve.
w in J (= Nm)
So P has to be in Pa = N/m
2
and V has to be in m
3
CM 1502 35
Irreversible or Reversible Work Paths?
1.
2.
CM 1502
Irreversible Processes
- piston was suddenly moved up by a substantial
amount in one step
webpages.marshall.edu/.../rev_irr_proc/rev.html
For example, expansion of a
gas in a cylinder by the
sudden removal of a mass
from the piston, assuming that
the piston slides without
friction and that no heat is
transferred.
Irreversible process as the
expansion cannot be
reversed without significant
external intervention.
P
ext
<< P
sys

CM 1502 37
Reversible Work Path
Expansion (P
ext
< P
sys
):
Reversible expansion work is achieved when P
ext
is only
infinitesimally less than the P
sys
. In effect, the P
ext
P
sys
.

For each infinitesimal step that the piston moves up, the volume of
the system increases and the P
sys
decreases, the piston will stop
when P
sys
= P
ext
. This is repeated.
Compression (P
ext
> P
sys
):
Reversible compression work is achieved when P
sys
is only
infinitesimally less than the P
ext
. In effect, the P
sys
P
ext
.

For each infinitesimal step that the piston is pushed down, the
volume of the system decreases and the P
sys
increases, the piston
will stop when P
sys
= P
ext
. This is repeated.
CM 1502 38
A reversible path is one during which the process can be reversed at
any point by an infinitesimal change of the variable that controls the
process. This is because variable external variable of system.

So, because P
ext
P
sys
, if one changes infinitesimally can
expansion (P
ext
< P
sys
) or
compression (P
ext
> P
sys
).
Process is reversible!

It proceeds with infinite reversible steps from its initial conditions to its
final conditions.

Reversible Work Path
CM 1502 39
Reversible Work Path
For reversible processes, w -P
ext
V, integrate:

w
rev
= -nRT ln(V
f
/V
i
)

i
f
V
V
V
V
V
V
V
V
nRTIn dV
V
1
nRT
dV
V
nRT
PdV w
f
i
f
i
f
i
= =
= =

Integrate 1/x = In x
CM 1502 40
Reversible Irreversible
Expansion Compression Expansion Compression
Expansion Compression
Irreversible Reversible Irreversible Reversible
4 situations:
1. Irreversible Expansion
2. Irreversible Compression
3. Reversible Expansion
4. Reversible Compression
1 (most work)
2
3
4 (least work)
Which gives more |work|?
vs. vs.
vs. vs.
CM 1502 41
http://chemistry.ucd.ie/notes/Unit3106/Thermo%20L7.ppt#6
Expansion
Compression
P-V Diagrams for Irreversible Work Paths
Which gives more |work|?
Expansion < Compression
w = -P
2
V
CM 1502 42
P-V Diagrams for Reversible Work Paths
P P
V V
Expansion
Compression
Which gives more |work|?
Expansion < Compression
w
rev
= -nRT ln(V
f
/V
i
)
CM 1502 43
P-V Diagrams for
Expansion: Irreversible work path Reversible work path

www.fordham.edu/.../Lectures/work_9133.html
One step irreversible process
Reversible process
Two step process
w
max
= w
rev
CM 1502 44
Expansion Reversible Work Path
V
P
CM 1502 45
Expansion: Irreversible work path Reversible work path
Proof that |w
rev
| > |w
irr
|.
www.fordham.edu/.../Lectures/work_9133.html
PV = nRT P = nRT/V
w = -P
2
V = -P
2
(V
final
V
initial
)
w = -P
2
(4V
1
V
1
) = -(nRT/4V
1
)(4V
1
V
1
)
w = -3/4 nRT
w = -P
2
(2V
1
V
1
) + -P
3
(4V
1
2V
1
)
w = -(nRT/2V
1
)(2V
1
V
1
) + -(nRT/4V
1
)(4V
1
2V
1
)
w = -nRT
w = -nRT ln(4V
1
/V
1
) = -nRT ln4
w = -1.39nRT
i
f
V
V
V
V
V
V
ln nRT - dV
V
nRT
- dV P - w
integrate curve, under area get To
f
i
f
i
= = =

Conclusion:
|w
rev
| > |w
irr
|
CM 1502 46
Compression: Irreversible work path Reversible work path
Proof that |w
rev
| < |w
irr
|.
w = -P
2
V = -P
2
(V
final
V
initial
)
w = -P
2
(V
1
4V
1
) = -(nRT/V
1
) (V
1
4V
1
)
w = +3 nRT
www.fordham.edu/.../Lectures/work_9133.html
PV = nRT P = nRT/V
w = -P
2
(2V
1
4V
1
) + -P
3
(V
1
2V
1
)
w = -(nRT/2V
1
) (2V
1
4V
1
) + -(nRT/V
1
) (V
1
2V
1
)
w = +2nRT
w = -nRT ln(V
1
/4V
1
)= -nRT ln
w = +1.39nRT
Conclusion:
|w
rev
| < |w
irr
|
2
1
3
1
2
1
2
i
f
V
V
V
V
V
V
ln nRT - dV
V
nRT
- dV P - w
integrate curve, under area get To
f
i
f
i
= = =

CM 1502 47
Reversible Irreversible
Expansion Compression Expansion Compression
Expansion Compression
Irreversible Reversible Irreversible Reversible
Which gives more |work|?
<
< >
Analogy:
1. Expansion small volume of gas vs. surroundings, pushing rock down hill, harder with many small steps
(reversible) compared to one large step (irreversible).
2. Compression hard to compress small volume of gas, pushing rock up hill, harder with one large step
(irreversible) compared to many small steps (reversible).
Approximates
below the curve
Approximates
above the curve
CM 1502 48
Heat
No exchange of matter and q
Can exchange w across boundary
Compared to closed systems,
same changes have a larger effect
on system because there is no
transfer of heat.
CM 1502 49
If V the same,
system is larger than for
isotherms (T is constant,
q can enter and be released)
Closed
system
CM 1502 50
When there is an adiabatic expansion (i.e. no q is loss), but U and T will
decrease due to the increase in volume, work done.

Likewise when there is an adiabatic compression (i.e. no q is gained),
but U and T will increase due to the decrease in volume, work done.

U and T change because w is done even though no q enters the
system.

1. U = q + w, U = w
(as q = 0).

2. U = C
v
n T

w
= C
v
n T, where C
v
is when no work is done (constant volume)
cf. w = -PV (only dependent on change in one variable).
w T
So, U = w
= C
v
n T
*
CM 1502 51
1/c
f
i
i f
c
f f
c
i i
f
i c
i
f
f
i c
i
f
v
f
i
i
f v
i
f
i
f
v
i
f
i
f
v
V
V
T
T
v
V
V
T
T
v
)
V
V
( T T or T V T V
V
V
)
T
T
(
V
V
In )
T
T
In(
then ,
R
C
c If
V
V
In
T
T
In
R
C
V
V
In -R
T
T
In C
V
V
ln -nR
T
T
nln C
T
w
dV
V
nR
- dT
T
n C
T
w
dV
V
nRT
- ndT C w
f
f
i
f
i
f
f
i
f
i
= =
=
=
=
=
=
= =
= =
= =

Irreversible:
U = w
= C
v
n T
w = -PV
i f f i
i
f
i
f
i
f
i
f
i
f
i
f
i
f
v i
f
i
f
i
f
v
v
v
p
v v
p
v
v p
T V T V
V
V
(
T
T
V
V
In(
T
T
In
V
V
In 1) (
T
T
In
V
V
In
C
R -
T
T
In
V
V
In -R
T
T
In C : into Subsitute
C
R
1
C
C
If
C
R
1
C
C
, C by Divide
R C C

=
=
=
=
=
=
=
=
=
=
1 1
1
1
)
)
,
w
=C
v
n T = -PV
CM 1502 52

i i f f
f
i
i i
f f
f
i
i i
f f
i
f
i i
f f
i
f
i i
f f
i
f
i i
f f
i i
f f
i i
f f
i
f
i i
i
f f
f
i
f
i
f
V P V P
V
V
V P
V P
V
V
(
V P
V P
V
V
(
V P
V P
V
V
(
V P
V P
V
V
(
V P
V P
Substitute
V P
V P
V P
nR
x
nR
V P
T
T
so
nR
V P
T and
nR
V P
T
V
V
(
T
T
=
=
=
=
=
=
= =
= =
=

1
1
) 1 (
) 1 (
1
1
1
)
)
)
)
,
)
Expressed in P and V
CM 1502 53
A cloud mass moves across the ocean at an altitude of 2 km and
encounters a coastal mountain range. As it rises to a height of 3.5 km to
pass the mountains, it undergoes an adiabatic reversible expansion.
The pressure at 2 km and 3.5 km is 0.802 and 0.602 atm, respectively. If
the initial temperature of the cloud is 288 K, will it rain or snow? Assume
that C
p,m
for air is 28.86 J K
-1
mol
-1
and air obeys the ideal gas law.
f
i
i f
f i
f f
i i
f
i
V
V
P T
P T
V P
V P
T
T
nRT PV
=
=
=

)
V
V
(
P
P
V P V P
f
i
i
f
i i f f
=
=
Have P
i
, P
f
and T
i
, need to find T
f
i f
f i
f
i
P T
P T
as
V
V
Sub
f
i
f
i / 1
i
f
i f
f i
i
f
T
T
P
P
)
P
P
(
)
P T
P T
(
P
P
=
=

1.4
R C
C
,
C
C
If
R C C
p
p
v
p
v p
=

= =
=

C 7.7 - K 265 T
T
288
0.602
0.802
)
0.802
0.602
(
f
f
4 . 1 / 1
= =
=
SNOW
CM 1502 54
Enthalpy of Compounds
Consider that, both ethanol and diethyl ether have the same
molecular formula C
2
H
6
O and number of bonds.

http://www.chem.ufl.edu/~itl/2045/lectures/lec_9be.html
5 x C-H
1 x C-C
1 x C-O
1 x O-H
6 x C-H
2 x C-O

CM 1502 55
Enthalpy of Compounds
BUT the energy content of these molecules is different:

Consider the Heats of Combustion (gas phase)

H
comb
(CH
3
CH
2
OH(gas)) = -1277.1 kJ mol
-1
H
comb
(CH
3
OCH
3
(gas)) = -1328.3 kJ mol
-1

WHY?

This difference in H is because there are different chemical
bonds in the two molecules!
CM 1502 56
Some Important Types of Enthalpy Change
heat of combustion (H
comb
)
heat of formation (H
f
)
heat of fusion (H
fus
)
heat of vaporization (H
vap
)
C
4
H
10
(l) + 13/2O
2
(g) 4CO
2
(g) + 5H
2
O(g)
K(s) + 1/2Br
2
(l) KBr(s)
NaCl(s) NaCl(l)
C
6
H
6
(l) C
6
H
6
(g)
Break bonds requires energy
(+ve, endothermic)

Form bonds releases energy
(-ve, exothermic)
CM 1502 57
Standard Enthalpies of Formation (H
f
)
The convention employed in thermochemistry is to take the
enthalpies of all elements in their standard states as zero.

Then the standard enthalpy of formation (H
f
) of a
compound is equal to the enthalpy change or the heat
evolved under constant pressure (H = q
p
), when forming
1 mole of the compound.
Standard (1 atm)
If T not stated, its 298K.

C + O
2
CO
2
0 0 -393.5 kJ mol
-1

H
f
(CO
2
) = -393.5 kJ mol
-1
CM 1502 58
The Eight Allotropes of Carbon
a) Diamond
b) Graphite (standard state)
c) Lonsdaleite
d) Buckministerfullerene (C60)
e) C540
f) C70
g) Amorphous carbon
h) Single-walled carbon
nanotube
http://en.wikipedia.org/wiki/Image:Eight_Allotropes_of_Carbon.png
H
f
(CO
2
)
C + O
2
CO
2
CM 1502 59
Elements in their Standard States
How do we decide which ones to use?

Carbon:
Graphite is the defined standard, it is more common and more
stable than diamond.

e.g. Hydrogen:
Most hydrogen exists at standard conditions as H
2
(g) [minute
amounts may exist as H (g)] so we choose the most common
form at normal (standard) conditions.

http://www.chem.queensu.ca/people/faculty/Mombourquette/FirstYrChem/thermo1/index.htm
CM 1502 60
Enthalpy of Reaction (H)
The standard enthalpy change of a reaction (H) can be readily
calculated from the known standard enthalpies of formation (H
f
) of
the compounds involved. Consider, for example, the reaction at 298 K:

CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O (l)
H
f
(kJ mol
-1
): -74.5 0 -393.5 -285.9

As is the standard practice, H of the products and reactants are
taken at the same temperature.

H = n H
f
(products) n H
f
(reactants)
= [-393.5 + (2 x -285.9)] [-74.5 + 0] = -890.7 kJ

Negative value of H shows that the enthalpy of the product molecules is
less than that of the reactants molecules => exothermic reaction

CM 1502 61
Figure 6.8
Enthalpy Diagrams for Exothermic and Endothermic Processes.
E
n
t
h
a
l
p
y
,

H

E
n
t
h
a
l
p
y
,

H

CH
4
+ 2O
2

CO
2
+ 2H
2
O
H
initial

H
initial
H
final

H
final

H
2
O(l)
H
2
O(g)
heat out heat in
H < 0 H > 0
A Exothermic process B Endothermic process
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g) H
2
O(l) H
2
O(g)
CM 1502 62
Hesss Law (part 1)
H = n H
f
(products) n H
f
(reactants)

also applies to other state functions
Germaine Henri Hess
CM 1502 63
Enthalpy of Reaction (H)
Conditions:

Able to directly measure H of some reactions by calorimetry.
For example, complete combustion reactions that is absent of
complicated side reactions like:

C (graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ (at 298 K)

Units not always kJ mol
-1
e.g. 2SO
2
(g) + O
2
(g) 2SO
3
(g) or SO
2
(g) + O
2
(g) SO
3
(g)
Units not always kJ mol
-1
especially if the stoichiometry is not 1.
H is for reaction as written.

CM 1502 64
Enthalpy of Reaction (H)
But there are many reactions which cannot be satisfactorily carried out in
a calorimeter. For example, the incomplete combustion reaction that has
the side reaction forming CO
2
. H for the formation of carbon monoxide
alone cannot be determined experimentally.

C (graphite) + O
2
(g) CO (g)

However, H of this reaction can be calculated using Hesss law (part 2):
the enthalpy (H) of a reaction is the sum of the H into which the
reaction may be divided.
(1) C (s) + O
2
(g) CO (g) H
1
= ?
(2) CO (g) + O
2
(g) CO
2
(g) H
2
= -283 kJ
(3) C (s) + O
2
(g) CO
2
(g) H
3
= -393.5 kJ

Elimination exercise: H
1
= (-H
2
) + H
3
= 283 + (-393.5) kJ = -110.5 kJ

Reaction reversed
(2) CO
2
(g) CO (g) + O
2
(g) H
2
= +283 kJ

CM 1502 65

Calculate the H of formation of acetylene C
2
H
2
:
2C (graphite) + H
2
(g) C
2
H
2
(g)
using equations for each step and the corresponding H:
(1) C (graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ
(2) H
2
(g) + O
2
(g) H
2
O (l) H = -285.8 kJ
(3) 2C
2
H
2
(g) + 5O
2
(g) 4CO
2
(g) + 2H
2
O (l) H = -2598.8 kJ

(1) x 4 4C (graphite) + 4O
2
(g) 4CO
2
(g) H = -1574 kJ
(2) x 2 2H
2
(g) + O
2
(g) 2H
2
O (l) H = -571.6 kJ
(3) reversed 4CO
2
(g) + 2H
2
O (l) 2C
2
H
2
(g) + 5O
2
(g) H = +2598.8 kJ

4C (graphite) + 2H
2
(g) 2C
2
H
2
(g) H = +453.2 kJ
2C (graphite) + H
2
(g) C
2
H
2
(g) H = +226.6 kJ
Halve no. of moles
Halve H
CM 1502 66
We can consider the reaction to occur in
- one step [T] or
- in three distinct steps [1], [2] and [3].
http://www.chem.queensu.ca/people/faculty/Mombourquette/FirstYrChem/thermo1/index.htm
The enthalpy change in a
reaction does not depend
on the reaction pathway
(because it is a state
function).
Hesss Law
CM 1502 67
T dependence of H and Kirchhoffs Law

H are tabulated refer to a particular temperature, usually 298K (25C).

So what happens if the reaction is run at 320 K? H is T dependent.

Kirchhoffs Law: H
T2
= H
T1
+ C
P
T
This law assumes that C
p
of reactants and products are independent of T.
C (graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ (at T
1
= 298 K)
C (graphite) + O
2
(g) CO
2
(g) H = ? kJ (at T
2
= 320 K)
There will be additional H. Hence, H
T2
= H
T1
+ H
We know H = C
P
nT and since now there is a chemical transformation from
reactants to products, we have C
P
= n C
P
(products) n C
P
(reactants)
CM 1502 68
Kirchhoffs Law: H
T2
= H
T1
+ C
P
T
C
p
C (s, graphite) = 8.527 J mol
-1
K
-1
C
p
O
2
(g) = 29.355 J mol
-1
K
-1
C
p
CO
2
(g) = 37.11 J mol
-1
K
-1

C (graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ (at T
1
= 298 K)
C (graphite) + O
2
(g) CO
2
(g) H = ? kJ (at T
2
= 320 K)
C
P
= -0.772 J mol
-1
K
-1

= -7.72 x 10
-4
kJ mol
-1
K
-1

H
T2
= -393.5 + -7.72 x 10
-4
(320 298)
= -393.52 kJ

Approximately additional 20 J released at the higher T.