Bomb CALORIMETRY is used to determine the enthalpy of combustion for hydrocarbons. The bomb is made from stainless steel, the combustion reaction occurs at constant volume and there is no work. The change in internal energy of the reactants upon combustion can be calculated from Since the process is constant volume, dV=0.
Bomb CALORIMETRY is used to determine the enthalpy of combustion for hydrocarbons. The bomb is made from stainless steel, the combustion reaction occurs at constant volume and there is no work. The change in internal energy of the reactants upon combustion can be calculated from Since the process is constant volume, dV=0.
Bomb CALORIMETRY is used to determine the enthalpy of combustion for hydrocarbons. The bomb is made from stainless steel, the combustion reaction occurs at constant volume and there is no work. The change in internal energy of the reactants upon combustion can be calculated from Since the process is constant volume, dV=0.
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.