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Question: State first law of thermodynamics and derive the relation between molar specific heats of a gas....

State first law of thermodynamics and derive the relation between molar specific heats of a gas.

Explanation

Solution

For finding relation between CP  and CV  {C_P}\;{\text{and }}{C_V}\;
Use the equation q = n C ΔTq{\text{ }} = {\text{ }}n{\text{ }}C{\text{ }}\Delta T, and apply for CP  and CV  {C_P}\;{\text{and }}{C_V}\;.
And also apply the fact that:
At constant pressure, change in heat = change in enthalpy i.e. Q=ΔHQ = \Delta H
At constant volume, change in heat = change in internal energy i.e. Q=ΔUQ = \Delta U

Complete step by step answer:
The first law of thermodynamics is nothing but the application of the principle of conservation of energy to heat energy and thermodynamic processes and systems.The first law of thermodynamics states that the heat added to the system minus the work done by the system is equal to the change in internal energy of the system.The standard unit for all these quantities is joule (J), but they are sometimes also expressed in calories, where calorie = 4.2 joules.
Relation between molar specific heats:
There are two molar specific heat values for a gas:
The molar heat capacity C, at constant volume, is represented by CV{C_V}.
At constant pressure, the molar heat capacity C, is represented by CP{C_P}.
In the following section, we will find how CP  and CV  {C_P}\;{\text{and }}{C_V}\;are related, for an ideal gas.
From the equation q = n C ΔTq{\text{ }} = {\text{ }}n{\text{ }}C{\text{ }}\Delta T, we can say:
At constant pressure P, we have
qP  = n CPΔT{q_P}\; = {\text{ }}n{\text{ }}{C_P}\Delta T
This value is equal to the change in enthalpy, that is,
qP  = n CPΔT = ΔH{q_P}\; = {\text{ }}n{\text{ }}{C_P}\Delta T{\text{ }} = {\text{ }}\Delta H---------------[1]
Similarly, at constant volume V, we have
qV  = n CVΔT{q_V}\; = {\text{ }}n{\text{ }}{C_V}\Delta T
This value of qv{q_v}, is equal to the change in internal energy of the system, that is,
qV  = n CVΔT = ΔU{q_V}\; = {\text{ }}n{\text{ }}{C_V}\Delta T{\text{ }} = {\text{ }}\Delta U---------------[2]
We know that for one mole of an ideal gas, when (n=1):

ΔH = ΔU + Δ(pV) (from ideal gas law PV = nRT = RT, for n = 1)   ΔH= ΔU + Δ(RT) = ΔU + R ΔT  Therefore,   ΔH = ΔU + R ΔT\Delta H{\text{ }} = {\text{ }}\Delta U{\text{ }} + {\text{ }}\Delta \left( {pV} \right){\text{ }}\left( {\because {\text{from ideal gas law PV = nRT = RT, for n = 1}}} \right)\; \\\ \Rightarrow \Delta H = {\text{ }}\Delta U{\text{ }} + {\text{ }}\Delta \left( {RT} \right){\text{ }} = {\text{ }}\Delta U{\text{ }} + {\text{ }}R{\text{ }}\Delta T \\\ \\\ {{\text{Therefore, }}\;\Delta H{\text{ }} = {\text{ }}\Delta U{\text{ }} + {\text{ }}R{\text{ }}\Delta T}

Substituting the values of \DeltaH and \DeltaU{\text{\Delta H and \Delta U}} from above in the former equation,[1] and [2]

CPΔT = CVΔT + R ΔT CP  = CV  + R CP   CV  = R \Rightarrow {C_P}\Delta T{\text{ }} = {\text{ }}{C_V}\Delta T{\text{ }} + {\text{ }}R{\text{ }}\Delta T \\\ \Rightarrow {C_P}\; = {\text{ }}{C_V}\; + {\text{ }}R \\\ \therefore {C_{P\;}}-{\text{ }}{C_V}\; = {\text{ }}R \\\

Note: Usually in chemistry texts they write the first law asΔU=Q+W\Delta U = Q + W. It is the same law, just the difference is that W is defined as the work done on the system instead of work done by the system.