Why is the change in enthalpy zero for isothermal processes?
Answer
555.9k+ views
Hint: An isothermal process may be a thermodynamic process during which the temperature of the system remains constant. Thus, the change in internal energy for an isothermal process is zero. For ideal gases, enthalpy is simply a function of temperature. As the temperature is constant in an isothermal process, change in enthalpy of the process is zero.
Complete answer:
An isothermal process is a thermodynamic process in which the temperature of the system remains constant. Thus, For an isothermal process \[PV = {\text{Constant}}\]. For ideal gases, the change in internal energy is zero for an isothermal process since an ideal gas has no interactions between particles, no intermolecular forces, so pressure change at constant temperature does not change internal energy.
For ideal gases, enthalpy is a function of the only temperature. Thus, in an isothermal process involving only ideal gases, the change in enthalpy is zero.
From the Maxwell Relation for the enthalpy for a reversible process in a thermodynamically-closed system,
\[{\text{dH = TdS + VdP}} - - - - - - \left( 1 \right)\]
Now, on infinitesimally varying the pressure at constant temperature, we get
\[{\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = T{\left( {\dfrac{{\partial S}}{{\partial P}}} \right)_T} + V{\left( {\dfrac{{\partial P}}{{\partial P}}} \right)_T} - - - - - - \left( 2 \right)\]
\[\left( {\dfrac{{\partial P}}{{\partial P}}} \right) = 1\]
Now we will examine the entropy term, the Gibbs' free energy is a function of temperature and pressure from its Maxwell Relation for a reversible process in a thermodynamically closed system:
\[dG = - SdT + VdP - - - - - \left( 3 \right)\]
Since the Gibbs' free energy (as with any thermodynamic function) is a state function, its cross-derivatives are equal
\[{\left( {\dfrac{{\partial S}}{{\partial P}}} \right)_T} = - {\left( {\dfrac{{\partial V}}{{\partial T}}} \right)_P} - - - - - \left( 4 \right)\]
Substituting \[\left( 4 \right)\] in \[\left( 2 \right)\] we get,
\[ \Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - T{\left( {\dfrac{{\partial V}}{{\partial T}}} \right)_P} + V\]
Using the ideal gas equation, we can say \[V = \dfrac{{nRT}}{P}\]
Substituting this in the above equation we get,
\[{\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - T\dfrac{\partial }{{\partial T}}{\left[ {\dfrac{{nRT}}{P}} \right]_P} + \dfrac{{nRT}}{P}\]
\[ \Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - \dfrac{{nRT}}{P}\dfrac{{\partial \left[ T \right]}}{{\partial T}} + \dfrac{{nRT}}{P}\]
\[\Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - \dfrac{{nRT}}{P} + \dfrac{{nRT}}{P}\]
\[\therefore {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = 0\]
Thus, for ideal gases enthalpy does not change for an isothermal process.
Note: When a process takes place at constant pressure, the heat absorbed or released is equal to the Enthalpy change. Enthalpy is the sum of the internal energy and the product of pressure and volume.Enthalpy can also be written as \[\Delta H = \Delta U + \Delta \left( {PV} \right)\].
Complete answer:
An isothermal process is a thermodynamic process in which the temperature of the system remains constant. Thus, For an isothermal process \[PV = {\text{Constant}}\]. For ideal gases, the change in internal energy is zero for an isothermal process since an ideal gas has no interactions between particles, no intermolecular forces, so pressure change at constant temperature does not change internal energy.
For ideal gases, enthalpy is a function of the only temperature. Thus, in an isothermal process involving only ideal gases, the change in enthalpy is zero.
From the Maxwell Relation for the enthalpy for a reversible process in a thermodynamically-closed system,
\[{\text{dH = TdS + VdP}} - - - - - - \left( 1 \right)\]
Now, on infinitesimally varying the pressure at constant temperature, we get
\[{\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = T{\left( {\dfrac{{\partial S}}{{\partial P}}} \right)_T} + V{\left( {\dfrac{{\partial P}}{{\partial P}}} \right)_T} - - - - - - \left( 2 \right)\]
\[\left( {\dfrac{{\partial P}}{{\partial P}}} \right) = 1\]
Now we will examine the entropy term, the Gibbs' free energy is a function of temperature and pressure from its Maxwell Relation for a reversible process in a thermodynamically closed system:
\[dG = - SdT + VdP - - - - - \left( 3 \right)\]
Since the Gibbs' free energy (as with any thermodynamic function) is a state function, its cross-derivatives are equal
\[{\left( {\dfrac{{\partial S}}{{\partial P}}} \right)_T} = - {\left( {\dfrac{{\partial V}}{{\partial T}}} \right)_P} - - - - - \left( 4 \right)\]
Substituting \[\left( 4 \right)\] in \[\left( 2 \right)\] we get,
\[ \Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - T{\left( {\dfrac{{\partial V}}{{\partial T}}} \right)_P} + V\]
Using the ideal gas equation, we can say \[V = \dfrac{{nRT}}{P}\]
Substituting this in the above equation we get,
\[{\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - T\dfrac{\partial }{{\partial T}}{\left[ {\dfrac{{nRT}}{P}} \right]_P} + \dfrac{{nRT}}{P}\]
\[ \Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - \dfrac{{nRT}}{P}\dfrac{{\partial \left[ T \right]}}{{\partial T}} + \dfrac{{nRT}}{P}\]
\[\Rightarrow {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = - \dfrac{{nRT}}{P} + \dfrac{{nRT}}{P}\]
\[\therefore {\left( {\dfrac{{\partial H}}{{\partial P}}} \right)_T} = 0\]
Thus, for ideal gases enthalpy does not change for an isothermal process.
Note: When a process takes place at constant pressure, the heat absorbed or released is equal to the Enthalpy change. Enthalpy is the sum of the internal energy and the product of pressure and volume.Enthalpy can also be written as \[\Delta H = \Delta U + \Delta \left( {PV} \right)\].
Recently Updated Pages
If x a + bt + ct2 where x is in meters and t is in class 11 physics CBSE

A car covers the first half distance between two places class 11 physics CBSE

The resultant of two vectors overrightarrow P and overrightarrow class 11 physics CBSE

Find the value of cos 135 class 11 maths CBSE

A mass M is held in place by an applied force F and class 11 physics CBSE

A solution of glucose in water is labelled as 10 dfracwv class 11 chemistry CBSE

Trending doubts
Find the value of the expression given below sin 30circ class 11 maths CBSE

One Metric ton is equal to kg A 10000 B 1000 C 100 class 11 physics CBSE

Draw a diagram of nephron and explain its structur class 11 biology CBSE

10 examples of friction in our daily life

Proton was discovered by A Thomson B Rutherford C Chadwick class 11 chemistry CBSE

Bond order ofO2 O2+ O2 and O22 is in order A O2 langle class 11 chemistry CBSE

