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http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
BOMB CALORIMETRY
1. Purpose of Bomb Calorimetry Experiments
Bomb calorimetry is used to determine the enthalpy of combustion, DcombH, for hydrocarbons: CxHYOz (s) + (2X+Y/2-Z)/2 O2 (g) X CO2 (g) + Y H2O (l) Since combustion reactions are usually exothermic (give off heat), DcombH is typically negative. (However, be aware that older literature defines the "heat of combustion" as -DcombH, so as to avoid compiling tables of negative numbers!)
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., qcalorimeter = 0 Since the bomb is made from stainless steel, the combustion reaction occurs at constant volume and there is no work, i.e., wcalorimeter = - p dV = 0 Thus, the change in internal energy, DU, for the calorimeter is zero DUcalorimeter = qcalorimeter + wcalorimeter = 0 The thermodynamic interpretation of this equation is that the calorimeter is isolated from the rest of the universe.
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Bomb Calorimetry
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
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 Cv yields
Assuming Cv to be independent of T over small temperature ranges, this expression can be integrated to give
where Cv is the heat capacity of the surroundings, i.e., the water and the bomb.
3. B. Enthalphy change DH
By definition of enthalpy
Since there is very little expansion work done by condensed phases, D(pV) 0 for solids and liquids. Assuming the gas to be ideal yields
In the case where Dngas < 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,
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Bomb Calorimetry
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
4. B. Measuring Cv
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 Cv are 1. Burning a standard with known DU, e.g., benzoic acid. mbenzoic acid DUbenzoic acid = mbenzoic acid -6318 cal/gK = -Cv DT 2. Doing electrical work by passing current though a resistor. DU = w + q = V I t + 0 = Cv DT
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Bomb Calorimetry
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
2Fe +
O2 Fe2O3
The heat released by combustion of the fuse is accounted for by recognizing that DU = DUsample msample + DUburned fuse mburned fuse = -Cv DT 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 (qcalorimeter 0) and the stirrer does work on the calorimeter (wcalorimeter 0). Nonadiabaticity is corrected for with an empirical radiative correction, RC.
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
Flushing the bomb with oxygen prior to firing, thereby displacing all nitrogen, eliminates nitric acid formation.
6. Application of DcombH
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
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Bomb Calorimetry
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
any reaction involving the compound. The enthalpy of combustion for the reaction can be written as DcombH(CxHyOz) = v(CxHyOz)DfH(CxHyOz) + v(O2)DfH(O2) + v(CO2)DfH(CO2) + v(H2O)DfH(H2O)
DcombH(CxHyOz) = v(CxHyOz)DfH(CxHyOz) + v(O2)DfH(O2) + v(CO2)DfH(CO2) + v(H2O)DfH(H2O) where v(i) is the stoichiometric coefficient of i. Since DfH(CxHyOz) and DfH(H2O) are known (and DfH(O2) equals zero), measurement of DcombH(CxHyOz) allows calcualtion of DfH(CxHyOz).
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Bomb Calorimetry
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
Solution Calorimeter Reactants are initially separated. The temperature change is measured when they are allowed to mix. Quantities that can be determined include DmixH, DdilutionH, and DsolvationH.
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.
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