Question
Question: Calculation of enthalpy and entropy of fusion of an unknown solid?...
Calculation of enthalpy and entropy of fusion of an unknown solid?
Solution
Entropy is the amount of intrinsic disturbance within a compound, while enthalpy is the amount of internal energy present in the compound. For elemental compounds like hydrogen and oxygen, enthalpy is zero; however, enthalpy is nonzero for water (regardless of phase).
Complete answer:
ΔSfus=5.52J/molK
ΔHfus=2.36kJ/mol
Explanation:
The Clapeyron equation in the form will be your tool of choice for this problem.
dTdP=ΔTfusΔSfus (i)
You now realise that the enthalpy change of fusion, ΔHf, and the entropy change of fusion, ΔSfhave the following relationship.
ΔSfus=TΔHfus (II)
The Gibb’s free energy transition at equilibrium is used to derive this.
ΔG=ΔH−TΔS
Since ΔG=0 in equilibrium, it follows that you have
ΔH=T⋅ΔS ⇒ΔS=TΔH
T will now reflect the melting temperature in your case. The average of the two melting temperatures is a reasonable rule of thumb to follow in this situation.
Taverage=2427.15K+429.26K=428.21K
You should now rearrange equation (i) to solve for dT and then integrate, but if you assume that the temperature shift, dT , is small enough, you can skip this stage.
You can get away with such an estimate because you're working on the solid-liquid phase line, which means minor temperature shifts are inevitable. If you go this way, you'll be able to tell that
dTdP≈ΔTΔP=ΔVfusΔSfus
You have everything you need to solve ΔSfus at this stage. You are aware, in particular, that
ΔT=T2−T1=2.11K
Here comes the tricky part - you need to convert ΔVfus and ΔP to cubic meters per mole, m3/mol,and pascals, Pa
ΔVfus=V2−V1 =156.6cm3−142.0cm3 =10.6cm3
This implies that you've
10.6molcm3⋅106cm31m3=10.6×10−6m3/mol
Finally, you have
ΔP=1.2×106Pa−1.01325×105Pa =10.987×105Pa
As a result, plug in these numbers and solve for ΔSfus
ΔSfus=ΔTΔP⋅ΔVfus
ΔSfus=2.11K10.987×105Pa×10.6×10−6molm3
This will equal to
ΔSfus=55.195×10−1KmolPam3
But, Pa×m3=J , so the answer will be
ΔSfus=5.52molKJ
Now, use the equation (ii) to get
ΔHfus=ΔSfus⋅Taverage ΔHfus=5.52mol⋅KJ⋅428.21K =2363.72molJ
This value will also be rounded to three sig figs, but expressed in kilojoules per mole.
ΔHfus=2.36kJ/mol
Note:
Now, the question can arise: Does enthalpy increase as entropy increases? As a result, an enthalpy shift will affect entropy. The external entropy (entropy of the surroundings) increases in an exothermic reaction. The external entropy (entropy of the environment) decreases in an endothermic reaction.