CHEM 1067

Introduction to Chemistry II
Lecture 5

Dr. Nigel John

Email: Nigel.John@sta.uwi.edu

Nigel John 2019

 Recap: Hess’s Law
Hess’s Law:
• states that regardless of the multiple stages or steps of a
reaction, the total enthalpy change (ΔH) for the reaction is
the sum of all changes.

• The standard enthalpy of a reaction, is the sum of the

standard enthalpies of the reactions into which the overall
reaction may be divided.

Nigel John 2019

Example 1: Hess’s Law

Nigel John 2019

(iii)

(iv)

Nigel John 2019

At 298 K:
ΔrH° = + 369.20 + (-483.64) = -114.4 kJ mol-1

Calculate the ΔrH° for the reaction at 400 K.

Apply Kirchhoff’s Law

Nigel John 2019

 Kirchhoff’s Law
• Temperature dependence of enthalpy change accompanying a
reaction

• Used to estimate the standard reaction enthalpies at different

temperatures

Nigel John 2019

Kirchhoff’s Law

When temperature is increased, the enthalpy

of the products and the reactants both
increase, but may do so to different extents

- The change in enthalpy depends on the heat

capacities of the substances

- the change in ΔrH° reflects the difference in

the changes of the enthalpies

Nigel John 2019

 Kirchhoff’s Law
 H   H 
Cp     C   

p
 T  P  T p
Integration from temperature T1 to T2

dH
 C P RE:
dT n dx = x
n+1
 x
n+1
+C

Therefore: 𝑑∆𝐻 = ∆𝐶𝑝 𝑑𝑇

 dx  x +C
H2 T2
H1
dH   C P dT
T1
where C = constant of integration

Assuming ∆CP is independent of temperature

Nigel John 2019
Kirchhoff’s Law

H2 T2

H1
dH   C P dT
T1

H2 T2
H1 d H  CP T1 dT

H HH 2
1
 C P T T12
T

H 2  H1  Cp  T2  T1 
 H 2  H1 + Cp  T2  T1  Kirchoff's Law

Nigel John 2019

Kirchhoff’s Law

For standard conditions; Kirchoff’s Law

 R H 20   R H10   R CP0 (T2  T1 )

Where  R C P   nCP ( products)   nCP (reac tan ts)

and n = stoichiometric number

Assumptions
(i) No phase transitions occur in the temperature range of Interest
(ii) ΔrCp is independent of temperature

Nigel John 2019

Kirchhoff’s Law Example 1
4 HCl (g) + O2 (g) → 2 Cl2 (g) + 2 H2O (g)
𝜃
∆𝑟 𝐻298𝐾 = - 114.4 kJ mol-1

Given the following Cp / (J K-1 mol-1)

HCl (g) = 29.12 O2(g) = 29.36 Cl2 (g) = 33.91 H2O (g) = 33.58
Calculate the ΔrH° for the reaction at 400 K.

Using the following equation

Δ R H 20 = Δ R H10 + Δ R CP0 (T2 -T1 )

ΔCp = Σ nCp (products) - Σ nCp (reactants)

= [(2 x 33.91) + (2 x 33.58)] – [(4 x 29.12) + (29.36)] = -10.86 J K-1 mol-1

Nigel John 2019

Kirchhoff’s Law Example 1

Δ R H 20 = Δ R H10 + Δ R CP0 (T2 -T1 )

• ΔrH400K = - 114.4 kJ mol-1 + [(-10.86 x 10-3 kJ K-1 mol-1)(102K)]

= -115.5 kJ mol-1

Nigel John 2019

Kirchhoff’s Law Example 2

1
H 2 ( g )  O2 ( g ) 
 H 2 O( g )
2

 R H 373
0
K ?

 R H 298 K    f H  products)     f H (reac tan ts)

0 0 0

 R H 0  241.82  (0  0) kJ mole1

 R C P   C P ( products)   C P (reac tan t )

Nigel John 2019

 Kirchhoff’s Law Example 2

 R CP   CP (products)   CP (reac tan t)

1
ΔR CP = [CP (H 2 O,g)] - [(CP (H 2 ,g) + C (O ,g)]
2 P 2

1
 R C P  33.58  ((28.84)  (29.37))  R CP   9.95 JK 1mol 1
2

Nigel John 2019