9/13/2017 Thermodynamics

Thermodynamics
3.4.8 Variation of Enthalpy of Reaction with
Temperature (Kirchhoff’s Equation)
The enthalpy and internal energy values vary with variation in temperature. Hence, the literature
values that are given for a particular temperature cannot be directly used for study at a different
temperature. It is therefore essential to understand the variation of these values with temperature.
In 1885 the scientist Kirchhoff gave a relationship between the heat of the reaction and temperature.
It is derived as follows.
Let us take a general reaction
vAA (g) + vBB (g) → vCC (g) + vDD (g)
Δ r H = (vCHm,C + vDHm,D) - (vAHm,A + vBHm,B)
To study the effect of variation of temperature on Δ r H, we should know the rate of change of Δ r H
with temperature. This is obtained by differentiating the equation with respect to T at constant P

= vCCP,m (C) + vDCP,m (D) - vACP,m (A) - vBCP,m(B)

(3.60)

d(∆H) = ΔCP dT Kirchhoff’s law (3.61)

Here, = molar heat capacity at constant pressure

and ∆CP = change of heat capacity in a chemical reaction.

From the Kirchhoff’s Law we can calculate the enthalpy change at any temperature if its value at
a specific temperature is known.
To calculate the heat of the reaction at constant volume, ∆U at varying temperatures we can
derive the Kirchhoff’s equation as

or dΔU = ∆CV dT (3.62)

On integrating the Kirchhoff’s law equations the ∆H and ∆U can be calculated at different
temperatures
Case I: Heat capacity is independent of temperature change

∆H(T2) − ∆H(T1) = ∆CP(T2−T1) (3.63)

Similarly,
∆U(T2) − ∆U(T1) = ∆CV(T2−T1) (3.64)

Case II: Heat capacity is dependent on temperature change Dependence of molar heat capacity on
temperature is given by the equation

CP,m= α +β T + γT2 (3.65)

Here α, β and γ are constants for a given substance. Therefore,

∆ CP = (vCαC + vDαD - vAαA - vBαB) + (vCβC + vDβD - vAβA - vBβB) T

+ (vCγC + νDγD − vAγA − νBγB) T 2

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9/13/2017 Thermodynamics

∆CP = ∆α + ∆βT + ∆γT2 (3.66)

Therefore, Kirchhoff’s law can be written as

d(∆H) = (∆α + ∆βT + ∆γT2 ) dT
On integrating

Equation 3.67 is used to calculate precisely the enthalpy of a reaction at any temperature T2, if the
value at T1 is known.

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