Enthalpy Change with Temperature

MT2050 Chemical Thermodynamics and Phase Equilibria

Dr Mudith Karunaratne

Department of Materials Engineering

Sri Lanka Institute of Information Technology

October 1, 2023

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Thermodynamics
• For common reactions, standard enthalpy change data are available
generally for 25 ◦ C.
• Often, data are needed for higher temperatures for many reasons.
• For example, many reactions are not fast enough at 25 ◦ C.
• Therefore it often becomes necessary to find out the enthalpy change
of the reactions at a higher temperature from the data at 25 ◦ C.
• Applying Cp = dH/dT for a chemical reaction occurring at a
constant pressure
Z T Z T
dH = Cp dT
298 298
Z T
HT − H298 = Cp dT
298

If Cp is constant
HT − H298 = Cp (T − 298)
Dr Mudith Karunaratne (SLIIT) Enthalpy Change with Temperature October 1, 2023 2/9
Thermodynamics

• If Cp varies with temperature, then Cp can be expressed using a

polynomial expansion.
• Normally, three terms in a polynomial is sufficient to describe the
heat capacity with accuracy.

Cp = A + BT + CT −2 + DT 2

Z T
HT − H298 = (A + BT + CT −2 + DT 2 ) dT
298
 
B 1 1
=A(T − 298) + (T 2 − 2982 ) − C − +
2 T 298
D 3
(T − 2983 )
3

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Thermodynamics
T =T ∆HT
R P

Temperature
RT RT
298 (Cp dT )R 298 (Cp dT )P

R P
T = 298K ∆H298
(Reactants) (Products)

Enthalpy change for a reaction at temperature T other than 298 K

Z T Z T
Σ(Cp dT )R + ∆HT = ∆H298 + Σ(Cp dT )P
298 298
Z T  
∆HT = ∆H298 + Σ(Cp )P − Σ(Cp )R dT
298
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Thermodynamics
Problem 1

Calculate the standard heat of formation of PbO from Pb and O2 at

227 ◦ C (500 K) from the following data:
◦
∆H298,PbO = −219.24 kJ/mol
Cp,PbO = 44.35 + (16.74 × 10−3 )T J/Kmol
Cp,Pb = 23.56 + (9.75 × 10−3 )T J/Kmol
Cp,O2 = 29.96 + (4.184 × 10−3 )T − (1.67 × 105 )T −2 J/Kmol

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Thermodynamics
Solution to problem 1

The reaction of formation of PbO from Pb and O2 :

1
Pb(s) + O2 (g) −−→ PbO(s) (1)
2
◦
for which ∆H298,(1) = −219.24 kJ
Z T  
∆HT = ∆H298 + Σ(Cp )P − Σ(Cp )R dT (2)
298
Z 500  
◦ ◦
∆H500,(1) = ∆H298,(1) + Σ(Cp )P − Σ(Cp )R dT (3)
298
Z 500  
◦ 1
= ∆H298,(1) + Cp,PbO − Cp,Pb − Cp,O2 dT (4)
298 2
(5)

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Thermodynamics
Solution to problem 1

Z 500 
◦
∆H500,(1) = − 219240 + {44.35 + (16.74 × 10−3 )T }−
298
{23.56 + (9.75 × 10−3 )T }−

1 −3 5 −2
{29.96 + (4.184 × 10 )T − (1.67 × 10 )T } dT
2
Z 500 
= − 219240 + {5.81 + (4.898 × 10−3 )T +
298

(0.835 × 105 )T −2 } dT

(4.898 × 10−3 )
= − 219240 + 5.81(500 − 298) + (5002 − 2982 )−
  2
5 1 1
(0.835 × 10 ) − = −217 558.4097 J = −217.56 kJ
500 298
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Thermodynamics
Solution to problem 1

• The standard enthalpy change of reaction (1)

1
Pb(s) + O2 (g) −−→ PbO(s)
2
at 227 ◦ C is −217.56 kJ.
• In other words, the standard heat of formation of PbO at 227 ◦ C is
−217.56 kJ/mol.

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Thermodynamics
Problem 2

Calculate the standard heat of formation of solid PbO from liquid Pb and
O2 gas at 527 ◦ C (800 K). The melting point of lead is 327 ◦ C (600 K) and
its latent heat of fusion is 4.81 kJ/mol. The molar heat capacity at
constant pressure of liquid Pb is (32.43 − 3.10 × 10−3 T )J/Kmol. Use the
other data given in Problem 1.

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