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Question: Calculation of enthalpy and entropy of fusion of an unknown solid?...

Calculation of enthalpy and entropy of fusion of an unknown solid?

Explanation

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\Delta {S_{fus}} = 5.52J/mol\,K
ΔHfus=2.36kJ/mol\Delta {H_{fus}} = 2.36kJ/mol
Explanation:
The Clapeyron equation in the form will be your tool of choice for this problem.
dPdT=ΔSfusΔTfus\dfrac{{dP}}{{dT}} = \dfrac{{\Delta {S_{fus}}}}{{\Delta {T_{fus}}}} (i)
You now realise that the enthalpy change of fusion, ΔHf\Delta {H_f}, and the entropy change of fusion, ΔSf\Delta {S_f}have the following relationship.
ΔSfus=ΔHfusT\Delta {S_{fus}} = \dfrac{{\Delta {H_{fus}}}}{T} (II)
The Gibb’s free energy transition at equilibrium is used to derive this.
ΔG=ΔHTΔS\Delta G = \Delta H - T\Delta S
Since ΔG=0\Delta G = 0 in equilibrium, it follows that you have
ΔH=TΔS ΔS=ΔHT  \Delta H = T \cdot \Delta S \\\ \Rightarrow \Delta S = \dfrac{{\Delta H}}{T} \\\
TT 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=427.15K+429.26K2=428.21K{T_{average}} = \dfrac{{427.15K + 429.26K}}{2} = 428.21K
You should now rearrange equation (i) to solve for dTdT and then integrate, but if you assume that the temperature shift, dTdT , 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
dPdTΔPΔT=ΔSfusΔVfus\dfrac{{dP}}{{dT}} \approx \dfrac{{\Delta P}}{{\Delta T}} = \dfrac{{\Delta {S_{fus}}}}{{\Delta {V_{fus}}}}
You have everything you need to solve ΔSfus\Delta {S_{fus}} at this stage. You are aware, in particular, that
ΔT=T2T1=2.11K\Delta T = {T_2} - {T_1} = 2.11K
Here comes the tricky part - you need to convert ΔVfus\Delta {V_{fus}} and ΔP\Delta P to cubic meters per mole, m3/mol,{m^3}/mol,and pascals, Papascals,{\text{ }}Pa
ΔVfus=V2V1 =156.6cm3142.0cm3 =10.6cm3  \Delta {V_{fus}} = {V_2} - {V_1} \\\ \,\,\,\,\,\,\,\,\,\,\,\, = 156.6c{m^3} - 142.0c{m^3} \\\ \,\,\,\,\,\,\,\,\,\,\,\, = 10.6c{m^3} \\\
This implies that you've
10.6cm3mol1m3106cm3=10.6×106m3/mol10.6\dfrac{{c{m^3}}}{{mol}} \cdot \dfrac{{1{m^3}}}{{{{10}^6}c{m^3}}} = 10.6 \times {10^{ - 6}}{m^3}/mol
Finally, you have
ΔP=1.2×106Pa1.01325×105Pa =10.987×105Pa  \Delta P = 1.2 \times {10^6}Pa - 1.01325 \times {10^5}Pa \\\ \,\,\,\,\,\,\,\, = 10.987 \times {10^5}Pa \\\
As a result, plug in these numbers and solve for ΔSfus\Delta {S_{fus}}
ΔSfus=ΔPΔTΔVfus\Delta {S_{fus}} = \dfrac{{\Delta P}}{{\Delta T}} \cdot \Delta {V_{fus}}
ΔSfus=10.987×105Pa2.11K×10.6×106m3mol\Delta {S_{fus}} = \dfrac{{10.987 \times {{10}^5}Pa}}{{2.11K}} \times 10.6 \times {10^{ - 6}}\dfrac{{{m^3}}}{{mol}}
This will equal to
ΔSfus=55.195×101PamKmol3\Delta {S_{fus}} = 55.195 \times {10^{ - 1}}{\dfrac{{Pam}}{{K\,mol}}^3}
But, Pa×m3=JPa \times {m^3} = J , so the answer will be
ΔSfus=5.52JmolK\Delta {S_{fus}} = 5.52\dfrac{J}{{mol\,K}}
Now, use the equation (ii) to get
ΔHfus=ΔSfusTaverage ΔHfus=5.52JmolK428.21K =2363.72Jmol  \Delta {H_{fus}} = \Delta {S_{fus}} \cdot {T_{average}} \\\ \Delta {H_{fus}} = 5.52\dfrac{J}{{mol \cdot K}} \cdot 428.21K \\\ \,\,\,\,\,\,\,\,\,\,\,\, = \,\,\,2363.72\dfrac{J}{{mol}} \\\
This value will also be rounded to three sig figs, but expressed in kilojoules per mole.
ΔHfus=2.36kJ/mol\Delta {H_{fus}} = 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.