Enthalpy - PDF 95

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Enthalpy is important topic for JEE Main and many time questions were asked from this topic so there
are some important definitions and numerical for revision of this topic. Most of the chemical reactions
take place at constant temperature and constant pressure.
For enthalpy, there is such not a definition, however, we can define Enthalpy (H) using the following
formula:
⇒ H = U + PV
Where, U = internal energy
P = pressure
V = Volume
There are two important points about enthalpy:
• Enthalpy is an extensive property.
Extensive Property: The measurable properties of a system which depends on size of system and amount
of matter present in the system.
• Enthalpy is a state function. Therefore, we cannot calculate its absolute value, but we can calculate the
change in enthalpy:
Change in enthalpy = ∆ H
⇒ ∆H = Hfinal – Hinitial
⇒ ∆H = nCp∆T =
We can have further two cases: if Cp depends on temperature and if Cp does not depend on temperature.
The only important case is when Cp is independent of temp.
⇒ ∆H = n Cp(T2-T1)
In the equation, Cp = molar heat capacity at constant pressure.
Relation between Enthalpy (∆H) and internal energy (∆U)

Since, H = U + PV
Let in the system at state 1: H1 = enthalpy, U1 = internal energy, P1 = pressure and V1 = volume
Let in the system at state 2: H2 = enthalpy, U2 = internal energy, P2 = pressure and V2 = volume
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Now, ∆H = H2 - H1
⇒ ∆H = (U2 + P2 V2) – (U1 + P1 V1)
⇒ ∆H = (U2 - U1) + (P2 V2 - P1 V1)
⇒ ∆H = ∆U + ∆(PV)
Conditions on the above equation:
• At constant volume: ∆H = ∆U + V∆P
• At constant pressure: ∆H = ∆U + P∆V
• The very important concept: For gaseous reaction
Since most of the reactions are generally takes place at constant temperature and pressure.
Ideal gas equation is, PV = nRT
Now using the same values in equation, ∆H = ∆U + ∆(PV)
⇒ ∆H = ∆U + ∆(nRT)
⇒ ∆H = ∆U + ∆ng. RT ⇒ This is an important formula.
Here ng = (total gaseous mole of product) – (total gaseous mole of reactant)
Let us calculate the value of ng for the following reaction:
N2 (g) + 3 H2 (g) → 2NH3 (g)
Gaseous moles of product (2NH3 (g)) = 2
Gaseous moles of reactant (N2 (g) + 3 H2 (g)) = 1+3 = 4
⇒ ng = 2 – 4 = -2
Example: Write the relation between ∆H and ∆U for the following reactions:
• C (s) + ½ O2 (g) → CO (g)
Solution: ng = 1 – ½ = ½
⇒ ∆H = ∆U + ½ RT
• H2 (g) + I2 (g) → 2HI (g)
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Solution: ng = 2 – 2 = 0
⇒ ∆H = ∆U
• C8H18 (l) + 25/2 O2 (g) → 8CO2 (g) + 9H2O (l)
Solution: C8H18 and 9H2O are not in gaseous state.
⇒ ng = 8 – 12.5 = - 4.5
⇒ ∆H = ∆U – 4.5 RT
Any system exchange heat at two conditions:
• At constant pressure (qP) (2) At constant volume (qV)
REMEMBER:
Heat exchange at constant pressure = enthalpy change
Heat exchange at constant volume = change in internal energy
Numerical 1: The enthalpy change for the reaction
N2 (g) + 3 H2 (g) → 2NH3 (g)
is -92.83 KJ at 298 K. Calculate the internal energy change.
(AIIMS 2006)
Solution: Given, ∆H = -92.38 KJ
⇒ ∆H = ∆U + ∆ng. RT
Because the unit is KJ so the value of R = 8.314
⇒ -92.38 KJ = [∆U – (2 × 8.314 × 298) / 1000] KJ
⇒ -92.38 = ∆U – 4.95 ⇒ ∆U = -92.38 + 4.95 = -87.42 KJ
Question: The heat of reaction for
C10H8 (s) + 12O2 (g) → 10CO2 (g) + 4H2O (l) at constant volume is -1228.2 Kcal at 25 degrees Celsius.
Calculate the heat of reaction at constant pressure.
Solution: qP = ∆H =? And qV = ∆U = -1228.2 Kcal
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We know that, ⇒ ∆H = ∆U + ∆ng. RT
⇒ ∆H = -1228.2 + [(-2 × 2 × 298)/ 1000] Kcal
⇒ ∆H = -1229.39 Kcal
Calculation of Cp and Cv
Before deriving the equation for Cp and Cv, let us understand the very basic and important terms:
Heat Capacity: The heat required to raise the temperature of a substance by 1 degree is called its heat
capacity.
Or
Capacity to store heat is known as heat capacity.
It is denoted by “C”.
Heat Capacity (C) = Heat exchanged / Change in temp
C = dq/dT
Unit for heat capacity = JK-1
Note: Heat capacity is an intensive property.
Specific Heat Capacity (s): Heat capacity per unit mass is known as specific heat capacity. We use this
in physics most of the times.
s=C/m
Unit of s = JK-1g-1
Note: Specific Heat capacity is an intensive property.
Molar Heat Capacity (Cm): Heat capacity per unit mole is defined as Molar heat capacity. It is an
intensive property.
Cm = C / n
Cm can be defined in two terms
1. Cp = molar heat capacity at constant pressure

2. Cv = molar heat capacity at constant volume
We know that Cm = C/n = dq/dT for one mole
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Therefore, (dq)p = dH ⇒ Cp = dH/dT
And (dq)v = dU ⇒ Cv = dU/dT
Degree of Freedom (f): The number of independent ways by which a system can exchange energy is
called degree of freedom of that system.
There are three types of degree of freedom:
• Translational degree of freedom (ft)

• Rotational degree of freedom (fr)
• Vibrational degree of freedom (fv)
Vibrational degree of freedom remains inactive at normal temperature. So, we deal with (ft) and (fr)
generally.
Points to Remember:
Cv = (fr) / R, where (fr) = degree of freedom
Cp – Cv = R for 1 mole of gas
Cp – Cv = nR for n mole gas
Poisson’s Ratio = Ɣ = Cp / Cv
And Cv = R / (Ɣ – 1)
These formulas will help you to solve numerical in the examination.
Click on the given link to attempt quiz:
Quiz on Thermodynamics
All the best!!
Team Gradeup
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Where, U = internal energy

There are two important points about enthalpy:

• Enthalpy is an extensive property.

The only important case is when Cp is independent of temp.

In the equation, Cp = molar heat capacity at constant pressure.

Relation between Enthalpy (∆H) and internal energy (∆U)

⇒ ∆H = (U2 + P2 V2) – (U1 + P1 V1)

⇒ ∆H = (U2 - U1) + (P2 V2 - P1 V1)

Conditions on the above equation:

• At constant volume: ∆H = ∆U + V∆P

• At constant pressure: ∆H = ∆U + P∆V

• The very important concept: For gaseous reaction

Ideal gas equation is, PV = nRT

Now using the same values in equation, ∆H = ∆U + ∆(PV)

⇒ ∆H = ∆U + ∆ng. RT ⇒ This is an important formula.

Here ng = (total gaseous mole of product) – (total gaseous mole of reactant)

Let us calculate the value of ng for the following reaction:

N2 (g) + 3 H2 (g) → 2NH3 (g)

Gaseous moles of product (2NH3 (g)) = 2

Gaseous moles of reactant (N2 (g) + 3 H2 (g)) = 1+3 = 4

• C (s) + ½ O2 (g) → CO (g)

• H2 (g) + I2 (g) → 2HI (g)

• C8H18 (l) + 25/2 O2 (g) → 8CO2 (g) + 9H2O (l)

Solution: C8H18 and 9H2O are not in gaseous state.

Any system exchange heat at two conditions:

• At constant pressure (qP) (2) At constant volume (qV)

Heat exchange at constant pressure = enthalpy change

Heat exchange at constant volume = change in internal energy

Numerical 1: The enthalpy change for the reaction

N2 (g) + 3 H2 (g) → 2NH3 (g)

is -92.83 KJ at 298 K. Calculate the internal energy change.

Solution: Given, ∆H = -92.38 KJ

Because the unit is KJ so the value of R = 8.314

⇒ -92.38 KJ = [∆U – (2 × 8.314 × 298) / 1000] KJ

⇒ -92.38 = ∆U – 4.95 ⇒ ∆U = -92.38 + 4.95 = -87.42 KJ

Question: The heat of reaction for

Solution: qP = ∆H =? And qV = ∆U = -1228.2 Kcal

We know that, ⇒ ∆H = ∆U + ∆ng. RT

⇒ ∆H = -1228.2 + [(-2 × 2 × 298)/ 1000] Kcal

Capacity to store heat is known as heat capacity.

Heat Capacity (C) = Heat exchanged / Change in temp

Unit for heat capacity = JK-1

Note: Heat capacity is an intensive property.

Note: Specific Heat capacity is an intensive property.

Cm can be defined in two terms

1. Cp = molar heat capacity at constant pressure

We know that Cm = C/n = dq/dT for one mole

Therefore, (dq)p = dH ⇒ Cp = dH/dT

And (dq)v = dU ⇒ Cv = dU/dT

There are three types of degree of freedom:

• Translational degree of freedom (ft)

Cp – Cv = R for 1 mole of gas

Cp – Cv = nR for n mole gas

These formulas will help you to solve numerical in the examination.

Click on the given link to attempt quiz:

All the best!!

Download Gradeup, the best JEE Main Preparation App

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