BOMB CALORIMETRY

http://www-ec.njit.edu/~grow/Bombcal/BombCalorimeter.html
1. Purpose of Bomb Calorimetry Experiments
Bomb calorimetry is used to determine the enthalpy of combustion,
comb
H, for hydrocarbons:
C
x
H
Y
O
z (s)
+ (2X+Y/2-Z)/2 O
2 (g)
X CO
2 (g)
+ Y H
2
O
(l)
Since combustion reactions are usually exothermic (give off heat),
comb
H is typically negative.
(However, be aware that older literature defines the "heat of combustion" as
comb
H, so as to
avoid compiling tables of negative numbers!)
2. Construction of a Bomb Calorimeter
thermometer
O
2
sample water
stirrer
ignition
unit
bomb
dewar
The bomb calorimeter consist primarily of the sample, oxygen, the stainless steel bomb, and
water.
The dewar prevents heat flow from the calorimeter to the rest of the universe, i.e.,
q
calorimeter
= 0
Since the bomb is made from stainless steel, the combustion reaction occurs at constant volume
and there is no work, i.e.,
w
calorimeter
= p dV = 0
Thus, the change in internal energy, U, for the calorimeter is zero
U
calorimeter
= q
calorimeter
+ w
calorimeter
= 0
The thermodynamic interpretation of this equation is that the calorimeter is isolated from the rest
of the universe.
3. U and H in a Bomb Calorimeter
3. A. Internal energy change U
Since the calorimeter is isolated from the rest of the universe, we can define the reactants
(sample and oxygen) to be the system and the rest of the calorimeter (bomb and water) to be the
surroundings.
The change in internal energy of the reactants upon combustion can be calculated from
1
]
1

,
_

+
,
_

+
dV
V
U
dT
T
U
dU dU
dU dU dU
T V
surr sys
surr sys tot
0
Since the process if constant volume, dV=0. Thus, recognizing the definition of heat capacity C
v
yields
dT C dU
v sys

Assuming C
v
to be independent of T over small temperature ranges, this expression can be
integrated to give
T C U
v
where C
v
is the heat capacity of the surroundings, i.e., the water and the bomb.
3. B. Enthalphy change H
By definition of enthalpy
) ( pV U H +
Since there is very little expansion work done by condensed phases, (pV) 0 for solids and
liquids. Assuming the gas to be ideal yields
gas
n RT U H +
3. C. Intuitive difference between U and H
Recall that U=q
v
is the heat flow under constant volume conditions, whereas H=q
p
is the heat
flow under constant pressure conditions. The difference between these two situations is that pV
work can be done under constant pressure conditions, whereas no pV work is done under
constant volume conditions.
Consider the case where n
gas
> 0. i.e., the system expands during the reaction. The same
amount of energy is released by the reaction under both sets of conditions. However, some of
the energy is released in the form of work at constant pressure; thus, the heat released will be less
than at constant volume. Mathematically,
U H
U H
>
<
< released energy released heat
In the case where n
gas
< 0. i.e., the system contracts during the reaction, the surroundings does
work on the system. Thus, this work is available for energy release from the system back to the
surroundings in the form of heat. Mathematically,
U H
U H
<
>
> released energy released heat
These cases can be depicted pictorially as follows:

n
gas
> 0
work done by system
H < U or H > U
q
v
= U
q
p
= w
const V
const p


n
gas
< 0
work done on system
H > U or H < U
q
v
= U
q
p
=
w
const V
const p
4. Calibration of the Calorimeter
4. A. Estimating C
v
The heat capacity of the bomb calorimeter can be estimated by considering the calorimeter to be
composed of 450 g water and 750 g stainless steel. Knowing the specific heat capacity of water
to be 1 cal/gK and estimating the specific heat capacity of steel to be 0.1 cal/gK yields
K
cal
525
K
cal
75
K
cal
450
K g
cal
1 . 0 g 750
K g
cal
1 g 450
) steel ( ) steel ( ) water ( ) water ( ) r calorimete (
v v v

,
_

,
_

+ C m C m C
4. B. Measuring C
v
For accurate work, the heat capacity of the calorimeter must be measured. This is done by
depositing a known amount of energy into the calorimeter and observing the temperature
increase. The two most common methods for measuring C
v
are
1. Burning a standard with known U, e.g., benzoic acid.

m
benzoic acid
U
benzoic acid
= m
benzoic acid
6318 cal/gK = C
v
T
2. Doing electrical work by passing current though a resistor.

U = w + q = VIt + 0 = C
v
T
5. Corrections in Bomb Calorimetry
5. A. Combustion of fuse
Nickel and iron fuses can burn according to
Ni +
2
1
O
2
NiO
or
2Fe +
2
3
O
2
Fe
2
O
3
The heat released by combustion of the fuse is accounted for by recognizing that

U = U
sample
m
sample
+ U
burned fuse
m
burned fuse
= C
v
T
where the mass of the burned fuse is determined by weighing the fuse before and after firing the
bomb.
5. B. Nonadiabaticity of calorimeter
A bomb calorimeter is only approximately adiabatic. In reality, there is a small heat leak through
the dewar (q
calorimeter
0) and the stirrer does work on the calorimeter (w
calorimeter
0).
Nonadiabaticity is corrected for with an empirical radiative correction, RC.
RC attempts
to make
areas equal
T
0 3 6 9 12 15 18
time (min)
T
The time at which the bomb is considered to be fired is the time that makes the areas indicated in
the above figure equal. For the Parr calorimeter, this is estimated to be at t = 7 minutes. Thus,
the temperature at t = 6 minutes must be extrapolated forward 1 minute by the pre-firing slope,
and the temperature at t = 12 minutes must be extrapolated backward 5 minutes by the post-firing
slope. Mathematically, this is done as follows
RC T T
T T T T
T T
T T T T
T T
T T
T
T T
T T

+

,
_

+
,
_

+
6 12
0 6 12 18
6 12
0 6 12 18
6 12
0 6
6
12 18
12
6
) ( ) ( 5
min 6
min) 1 (
min 6
min) 5 (
min 6
min) 1 (
min 6
min) 5 (
5. C. Nitric acid formation
At high temperatures, nitrogen can form nitric acid in the presence of oxygen and water. (This
reaction also occurs in automobile engines and is partially responsible for smog production.)
N
2
+
2
5
O
2
+ H
2
O 2HNO
3
Flushing the bomb with oxygen prior to firing, thereby displacing all nitrogen, eliminates nitric
acid formation.
6. Application of
comb
H
In addition to measuring the energy release of one particular reaction, calorimetry is an important
tool for determining the enthalpy of formation for the compound under study. This information
can then be applied to any reaction involving the compound.
The enthalpy of combustion for the reaction

can be written as

comb
H(C
x
H
y
O
z
) = v(C
x
H
y
O
z
)
f
H(C
x
H
y
O
z
) + v(O
2
)
f
H(O
2
) +
v(CO
2
)
f
H(CO
2
) + v(H
2
O)
f
H(H
2
O)

comb
H(C
x
H
y
O
z
) = v(C
x
H
y
O
z
)
f
H(C
x
H
y
O
z
) + v(O
2
)
f
H(O
2
) + v(CO
2
)
f
H(CO
2
) +
v(H
2
O)
f
H(H
2
O)
where v(i) is the stoichiometric coefficient of i. Since
f
H(C
x
H
y
O
z
) and
f
H(H
2
O) are known
(and
f
H(O
2
) equals zero), measurement of
comb
H(C
x
H
y
O
z
) allows calcualtion of

f
H(C
x
H
y
O
z
).
7. Other Types of Calorimeters
There are many kinds of calorimeters, each designed for measuring the heat released by a
particular chemical process. Some examples include:
Flame Calorimeter
The combustible gas is metered into the
calorimeter. Temperatures of all reactants
must be controlled. Since the reaction
occurs at constant pressure,
comb
H is
measured directly.

Solution Calorimeter
Reactants are initially separated. The
temperature change is measured when they
are allowed to mix. Quantities that can be
determined include
mix
H,
dilution
H, and

solvation
H.
Calorimeter design is very tricky, especially for processes involving very small energy changes,
e.g., protein folding, or energy changes on top of a large background, e.g., excess heat from
"cold fusion". Heat leaks must be minimized, and all other heat generating processes must be
accounted for.