20.110J / 2.772J / 5.

601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 1

Thermochemistry
Much of thermochemistry is based on finding easy paths to
calculate changes in enthalpy, i.e. understanding how to work
with thermodynamic cycles.

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 (the complete transfer from reactants

to products, not to some equilibrium state).
Fe2O3(s,T,p) + 3H2(g,T,p) = 2Fe(s,T,p) + 3H2O(l,T,p)

e.g.

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

2

2 3

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

We cannot know H values because enthalpy, like energy, is not an

absolute scale. We can only measure differences in enthalpy.

Define a reference scale for enthalpy

H (298.15K, 1 bar) 0

e.g.

For every element in its most stable

form at 1 bar and 298.15K

HH (g) (298.15K ) = 0
2

HC(graphite) (298.15K ) = 0

The means 1 bar

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Hf (298.15K ) :

Lecture #5

page 2

The heat of formation is the heat of reaction

to create 1 mole of that compound from its constituent elements in

their most stable forms.
Example (T = 298.15 K)
H2 (g,T,1 bar) + Br2 (l,T,1 bar) = HBr (g,T,1 bar)

Hf,HBr (T ) = Hrx (T ,1bar ) = HHBr

( g,T )

1
1
HH2 ( g,T ) HBr2 ( l,T )
2
2

 


0 - elements in most stable forms

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

We can calculate Hrx (298.15K ) for any reaction.
e.g. (T=298.15K)
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 [An example of a thermodynamic cycle applied

to thermochemistry]

Reactants

H rx

i Hf,i ( reactants )
i

Products

i i Hfi ( products )
,

Elements

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 3

CH4 (g,T,1 bar) = Cgraphite (s,T,1 bar) + 2H2(g,T,p)

HI
2O2 (g,T,1 bar) = 2O2 (g,T,1 bar)
HII
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)

Hrx = HI + HII + HIII + HIV

HI = HC + 2HH HCH = Hf,CH

2

HII = HO HO = 0
2

HIII = HCO HC HO = Hf,CO

2

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

2

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

2

In general,

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

i

stoichiometric coefficient

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

The heat of reaction is the heat flowing into the

reaction from the surroundings

If

Hrx < 0,

qp < 0

heat flows from the reaction to

the surroundings (exothermic)

If

Hrx > 0,

qp > 0

heat flows into the reaction from

the surroundings (endothermic)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 4

Calorimetry
The objective is to measure
Reactants (T1)

Hrx (T1 )

isothermal

constant p

Constant pressure

Products (T1)

(for solutions)

adiabatic
constant p

reaction
calorimeter

React. (T1) + Cal. (T1)

Hrx

Prod. (T1) + Cal. (T1)

constant p

HI
adiabatic

HII
constant p

constant p

Prod. (T2) + Cal. (T2)

I)

HI

React. (T1) + Cal. (T1)

II)

HII

Prod. (T2) + Cal. (T2)

adiabatic

constant p

constant p

Prod. (T2) + Cal. (T2)

Prod. (T1) + Cal. (T1)

______________________________________________________

Hrx (T1 )

React. (T1) + Cal. (T1)

constant p

Hrx (T1 ) = HI + HII

Prod. (T1) + Cal. (T1)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 5

(I) Purpose is to measure (T2 - T1)

Adiabatic, const. p

qp = 0

H I = 0

(II) Purpose is to measure heat qp needed to take prod. + cal.

from T2 back to T1.
T1

qp = C p ( Prod . + Cal .) dT = HII

T2

T2

Hrx (T1 ) = T C p ( Prod . + Cal . )dT

1

Constant volume

(when gases involved)

adiabatic
constant V

reaction
calorimeter

React. (T1) + Cal. (T1)

Urx

Prod. (T1) + Cal. (T1)

constant V

UI
adiabatic

UII
constant V

constant V

Prod. (T2) + Cal. (T2)

I)

U I

React. (T1) + Cal. (T1)

II)

UII

Prod. (T2) + Cal. (T2)

adiabatic

constant V

constant V

Prod. (T2) + Cal. (T2)

Prod. (T1) + Cal. (T1)

______________________________________________________

Urx (T1 )

React. (T1) + Cal. (T1)

constant V

Prod. (T1) + Cal. (T1)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 6

Urx (T1 ) = UI + UII

(I) Purpose is to measure (T2 - T1)

Adiabatic, const. V

qV = 0

UI = 0

(II) Purpose is to measure heat qV needed to take prod. + cal.

from T2 back to T1.
T1

qV = CV ( Prod . + Cal . )dT = UII

T2

T2

Urx (T1 ) = T CV ( Prod . + Cal . )dT

1

Now use

H = U + pV

or

H = U + ( pV

Assume only significant contribution to ( pV

( pV ) = R (nT

Ideal gas

Isothermal

T =T1

)
is from gases.

( pV ) = RT1 ngas

Hrx (T1 ) = Urx (T1 ) + RT1 ngas

T2

Hrx (T1 ) = CV ( Pr od . + Cal . ) dT + RT1 ngas

T1

e.g.

4 HCl(g) + O2(g) = 2 H2O(l) + 2 Cl2(g)

T1 = 298.15 K
Urx (T1 ) = -195.0 kJ

ngas = -3 moles

Hrx (T1 ) = -195.0 kJ + (-3 mol)( 298.15 K)(8.314x10-3 kJ/K-mol)

= -202.43 kJ

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #5

page 7

Temperature dependence of Hrx

Suppose know Hrx at some temperature T1 (e.g. at 298.15 K) and we

want to know it at some other temperature T2.
Generally the difference is small often we assume that there is no
temperature dependence if the difference between T1 and T2 is
small. If the difference between T1 and T2 is large enough, we can
calculate Hrx(T2) from the heat capacities of the reactants and
products (assuming no phase change in any component).

Hrx (T2 )

Reactants (T2)

constant p

Products (T2)

HI

HII
constant p

constant p

Hrx (T1 )

Reactants (T1)

constant p

Products (T1)

Hrx (T2 ) = HI + Hrx (T1 ) + HII

T1

T2

T2

T1

Hrx (T2 ) = Hrx (T1 ) + C p (react .)dT + C p ( prod .)dT

T2

Hrx (T2 ) = Hrx (T1 ) + C p ( prod .) C p (react .) dT

T1

T2

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

T1