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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #6

page 1

Thermochemistry
Goal: To predict H for every reaction, even if it cannot be carried out in the laboratory

The heat of reaction

Hrx

is the H for the isothermal

reaction at constant pressure. e.g. Fe2O3(s,T,p) + 3H2(g,T,p) = 2Fe(s,T,p) + 3H2O(l,T,p)

Hrx (T , p ) = 2HFe (T , p ) + 3HH O (T , p ) 3HH (T , p ) HFe O (T , p )

2 2 2 3

[Hrx = H ( products ) H ( reactants )]

We cannot know H values because enthalpy, like energy, is not measured on an absolute scale. We can only measure differences in enthalpy. Define a reference scale for enthalpy

H (298.15K, 1 bar) 0

For every element in its most stable form at 1 bar and 298.15K The means 1 bar

e.g.

HH (g) (298.15K ) = 0
2

HC (graphite) (298.15K ) = 0

Hf (298.15K ) :

We can now write reactions to form every compound from its constituent atoms. The heat of reaction is the heat of formation of 1 mole of that compound from the constituent elements in their most stable forms.

5.60 Spring 2008

Lecture #6

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Example (let T = 298.15 K) H2 (g,T,1 bar) + Br2 (l,T,1 bar) = HBr (g,T,1 bar)

Hrx = Hf ( products ) Hf ( reactants )

= Hf ,HBr ( g,T ) 1 1 Hf,H2 ( g,T ) Hf,Br2 (l ,T ) = Hf,HBr ( g,T 2 2   

0 - elements in most stable forms

We can tabulate Hf (298.15K ) values for all known compounds.

We can calculate Hrx (T ) for any reaction (T = 298.15K).

e.g.
CH4 (g,T,1 bar) + 2O2 (g,T,1 bar) = CO2 (g,T,1 bar) + 2H2O(l,T, 1 bar)
First decompose reactants into elements Second put elements together to form products Use Hesss law [A statement of the fact that because H is a function of state, we can add Hs around paths.] CH4 (g,T,1 bar) = Cgraphite (s,T,1 bar) + 2H2(g,T,p) HI HII 2O2 (g,T,1 bar) = 2O2 (g,T,1 bar) Cgraphite (s,T,1 bar) + O2 (g,T,1 bar) = CO2 (g,T,1 bar) HIII 2H2(g,T,p) + O2 (g,T,1 bar) = 2H2O(l,T, 1 bar) HIV ____________________________________________ CH4 (g,T,1 bar) + 2O2 (g,T,1 bar) = CO2 (g,T,1 bar) + 2H2O(l,T, 1 bar)

5.60 Spring 2008

Lecture #6

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Hrx = HI + HII + HIII + HIV

HI = HC + 2HH HCH = Hf,CH HII = HO HO = 0

2 2 2 2 4

HIII = HCO HC HO = Hf,CO

2 2 2 2

HIV = 2HH O 2HH HO = 2Hf,H O

2

Hrx = 2Hf,H O + Hf,CO Hf,CH

2 2

In general,

Hrx = i Hf,i (products ) i Hf,i (reactants )

i i

stoichiometric coefficient

H at constant p and for reversible process is H = q p

The heat of reaction is the heat flowing into the reaction from the surroundings
Hrx < 0,
q p < 0

If

heat flows from the reaction to the surroundings (exothermic)

If

rx > 0, H

qp > 0

heat flows into the reaction from the surroundings (endothermic)

5.60 Spring 2008

Lecture #6

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Temperature dependence of Hrx Recall

H = Cp T p

H = C p = i C p ,i (products ) i C p ,i (reactants )
T p i i

e.g.
CH4 (g,T,1 bar) + 2O2 (g,T,1 bar) = CO2 (g,T,1 bar) + 2H2O(l,T, 1 bar)

C p = C p ,CO2 ( g, T , 1 bar ) + 2C p ,H2O (l , T , 1 bar ) C p ,CH4 ( g, T , 1 bar ) 2C p ,O2 ( g, T , 1 bar )

T2
1

H dT = H (T2 ) H (T1 ) T p   

C p

H (T2 ) = H (T1 ) + C pdT

T1

T2

Especially simple when C p is T-independent