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Higher (HHV) and Lower (LHV) Heating values

Fuel HHV MJ/kg HHV BTU/lb HHV kJ/mol


Methane 55,5 23,900 889
Methanol 22.7 9,800 726
Ethane 51.90 22,400 1,560
Ethanol 29.70 12,800 1,300
Gasoline 47.30 20,400
Propane 50.35 21,700 2,220
Propanol 33.60 14,500 2,020




BOMB CALORIMETRY

1. Purpose of Bomb Calorimetry Experiments

Bomb calorimetry is used to determine the enthalpy of combustion,
comb
, for hydrocarbons:
C
x
H
Y
O
z (s,l,g)
+ (2X+ Y-Z) O
2 (g)
X CO
2 (g)
+ Y H
2
O
(l)
+
comb


2. Construction of a Bomb Calorimeter

The bomb calorimeter consist 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.,
Adiabatic 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.,
Isochor 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
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

Since the process if constant volume, dV=0. Thus, recognizing the definition of heat
capacity C
v
yields

Assuming C
v
to be independent of T over small temperature ranges, this expression can be
integrated to give

where C
v
is the heat capacity of the surroundings, i.e., heat capacity of the bomb, the water and
the bomb.
Before the bomb can be used to determine heat of combustion of any compound, it must be calibrated.
The value of C
v
can be estimated by C
v
(calorimeter) = m (water). C
v
(water) + m (steel). C
v
(steel)
m (water) and m (steel) can be measured;
C
v
(water)= 1 cal/g.K
C
v
(steel)= 0.1 cal/g.K
In laboratory, C
v
is determined by running a compound with known heat of combustion value:
C
v
= H
comb
/T
Common compounds are benzoic acid (H
comb
= 6318 cal/g) or p-methyl benzoic acid (H
c
= 6957 cal/g).
Temperature (T) is recorded every minute and T = T(final) - T(initial)





Enthalphy change H
By definition of enthalpy

Since there is very little expansion work done by condensed phases, (pV) 0 for solids and
liquids. Assuming the gas to be ideal yields


4. Calibration of the Calorimeter
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/g K and estimating the specific heat capacity of steel to be 0.1 cal/g K yields

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
Burning a standard with known U, e.g., benzoic acid.

m
benzoic acid
U
benzoic acid
= m
benzoic acid
6318 cal/g K = C
v
T

5. Corrections in Bomb Calorimetry
Combustion of fuse
Nickel fuses can burn according to
Ni + O
2
NiO + 981.3 cal/g
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.

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).

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.

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
+ (5/2) O
2
+ H
2
O 2HNO
3
+ 207 kJ/mol
Flushing the bomb with oxygen prior to firing, thereby displacing all nitrogen, eliminates nitric
acid formation.