NOTES ON CALORIMETRY

- Science of measuring heat (q) evolved or absorbed for a chemical or

physical change of state

(A) If the change of state is occurring in an open vessel (i.e. at constant pressure):
heat = qp = H
(B) If the change of state is occurring in a closed vessel (i.e. at constant volume):
heat = qV = U

When substances react with oxygen, they burn (combustion)

Products of combustion??
For example, at high pressures of oxygen:
C10H8(s) + 12 O2(g) 10CO2(g) + 4 H2O(l) + heat
Consider this reaction at constant volume: qV = U (Difference in internal energy
between initial and final states)
Assume U = Uo (i.e. it is independent of pressure)
Relationship between enthalpy and internal energy:
Ho = Uo + (pV) = Uo + (nRT)
Where the latter term includes the change in the number of moles of gas
(products reactants).
For the above combustion process:
Ho = Uo 2RT
Bomb Calorimetry Experiment: Measurement of the heat of combustion of an
aromatic hydrocarbon (Ho )
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(a) A bomb (stainless steel high pressure vessel containing sample and oxygen at
high pressure) is immersed in a jacketed bucket holding a known (fixed)
quantity of water.
(b) The sample is ignited and burned, and the temperature rise in the water is
measured:
fuse

dT

dt f

fuse
O2
Resistive
Heating
(ignition)

dT

dt i

Sample/pellet

NOTE: Both iron wire and sample will burn. Therefore, you must account for
any iron that is not burned (mass left in bottom of bomb) and substract
what did burn from your measurement.

(c) To relate a measured temperature change (K) to joules of energy evolved, need
the energy equivalent of the calorimeter (J/K)

E (J/K) =

Q b (m b ) + c Fe
T

Where: Qb = heat of combustion of a known (benzoic acid) (energy/g)

mb = mass of known
cFe = J of combusion of burned iron fuse (calculated from the mass of
iron burned and the specific heat of combustion of iron)

(d) The heat of combustion of an unknown can then be calculated:

E (J/K) =

Q s (m s ) + c Fe
T

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NOTE: The energy equivalent of the calorimeter depends on the volume of

water in the bath. Therefore, keep this fixed!

DO:
3 combustion reactions with a known and 3 combustion reactions with an
unknown.
NOTE:
(1) Each mass will have an error associated with it (from your uncertainty in the
balance reading);
(2) Each T will have an error associated with it (from your estimation of initial
and final slopes)
(3) For the benzoic acid, each run will result in E E.
(4) You are doing 3 runs, therefore when you average the Es, you must error
propagate the Es.
(5) Now have an E E in hand.
(6) Each run of the unknown produces a Qs Qs. (after error propagating the
E, m, and T)
(7) The error in your final value must be propagated from averaging the (Qs
Qs) (see point #4).
Report the enthalpy of combustion in kJ/mole
Evaluate the enthalpy of formation of the unknown and identify it based on
published values.

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