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The enthalpy changes for chemical reaction can be deduced for a range of
temperature.
For a chemical equation:
Reactants ---- Products
The enthalpy change for the reaction can be written as:
H = Hprod - Hreact
Where the product and reactants enthalpies imply the sum of the molar
enthalpies of the products and reactants in given chemical equation.
The derivative with respect to temperature is given as:
[(H) / T]P
= H T - H T
2
T1
T2
Cp dT
T1
Since,
Cp = a + bT + (C/T2)
Thus, we have
H T - H T =
2
T2
Cp dT
T1
H T =
Cp dT + const.
And
-110.52
-241.82
-393.51
= -41.17 kJmol-1
a terms
b terms
c terms
a = 12.55
b = -2.34 10-3
b = -7.66 105
We have
(U - U0)trans = (3/2) RT
The heat-capacity contribution for translational motion is
(U - U0)rot = (2/2)RT = RT
The heat-capacity contribution for rotational motion is
Crot = (U - U0)rot /T = R
The vibrational motion gives thermal energy of RT [ x / (ex-1)] per degree
of freedom where x = (vib / kT ).
(U - U0)vib = RT [ x / (ex-1)]
where x = (vib / kT )
Cp = Cv + R
= (5/2) R + Cvib + R
where x = (vib / kT )
= (7/2) R + Cvib
= 29.10 J K-1 mol-1 + Cvib
Non-linear molecules:
For non-linear molecules there are 3 rotational degrees of freedom, giving
rotational heat-capacity contribution as (3/2)R and (3n-6) vibrational degrees
of freedom, giving vibrational heat-capacity contribution as Cvib.
Thus
The total heat capacity contribution for non-linear diatomic molecules (1
mole of ideal gas) is given as:
Cp = Cv + R
= 3 R + Cvib + R
= 4 R + Cvib
= 33.26 J K-1 mol-1 + Cvib
where x = (vib / kT )
Thermal Enthalpy:
Thermal enthalpy means the enthalpy that a sample has as a result of
quantum states with energies greater than the lowest-energy, or ground, state
being occupied.
At 0 K, only the lowest energy states are occupied and the thermal energy is
zero.
The thermal enthalpy at other temperatures can be expressed as
T
H0T - H00 =
C0p dT
0
(U - U0)trans = (3/2) RT
(U - U0)rot = RT
(U - U0)vib = RT [ x / (ex-1)]
where x = (vib / kT )
At 298 K
x = (vib / kT ) = (1.10 10-20 J) / (1.381 10-23 JK-1 298 K)
= (1.10 103 ) / (1.381 298) = 2.67
[ x / (ex-1)] = 2.67 / (14.43 -1) = 0.198
At 1000 K
x = (vib / kT ) = (1.10 10-20 J) / (1.381 10-23 JK-1 1000 K)
= (1.10 103 ) / (1.381 1000) = 0.797
[ x / (ex-1)] = 0.797 / (2.218 -1) = 0.654
Now,
(U - U0) =(U - U0)trans + (U - U0)rot + (U - U0)vib
= (3/2) RT + RT + RT [ x / (ex-1)]
At 298 K
(U - U0)
= (3/2) RT + RT + RT 0.198
= 2.69 RT
= (2.69) ( 8.314 J K-1 mol-1) (298 K)
= 6684.48 J mol-1 = 6.68 kJ mol-1.
At 1000 K
(U - U0) = (3/2) RT + RT + RT 0.654
= 3.15 RT
= (3.15) ( 8.314 J K-1 mol-1) (1000K)
= 26189.10 J mol-1 = 26.18 kJ mol-1.
Now,
(H - H0) = (U - U0) + RT
AT 298 K
(H - H0) = (U - U0) + RT = 6684.48 J mol-1 + ( 8.314 J K-1 mol-1) (298 K)
= 6684.48 J mol-1 + 2477.57 J mol-1 = 9162.05 J mol-1 = 9.16 k J mol-1
AT 1000 K
(H - H0) = (U - U0) + RT = 26189.10 J mol-1 + ( 8.314 J K-1 mol-1) (1000 K)
= 26189.10 J mol-1 + 8314.00 J mol-1 = 34503.10 J mol-1= 34.5 k J mol-1