STANDARD THERMODYNAMIC FUNCTIONS

Chemical reaction

aA + bB

cC + dD

Equilibrium

aA + bB = cC + dD
Need to define the zeros from which things are measured! (e.g., sea level, center of earth) Standard sates of pure substances (denoted by superscript ) Solid and liquid: P = 1 bar and temperature = T Gas: P = 1 bar, temperature = T, ideal gas

Hm,200 Vm,200
molar quantity

H200
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STANDARD THERMODYNAMIC FUNCTIONS

Standard enthalpy of a reaction

Hrxn,T aA1 + bA2

HT

cA3 + dA4

HT = cHm,T (A3 ) + dHm,T (A4 )

aHm,T (A1 )

bH m, T (A2 )

HT =

3 Hm,T (A3 )

4 Hm,T (A4 )

1 Hm,T (A1 )

2H

m, T (A2 )

HT =
i

i Hm,T (Ai )
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STANDARD THERMODYNAMIC FUNCTIONS

Standard enthalpy of a reaction

HT =
i

i Hm,T (Ai )

Hm,T (Ai ) = Um,T (Ai ) =

molar enthalpy of Ai in its standard state at temperature T

molar internal energy of Ai in its standard state at temperature T

Not measurable Not interesting Only changes matter!

HT
tabulated, but not for every reaction...

STANDARD THERMODYNAMIC FUNCTIONS

Standard enthalpy of formation (tabulated, at least for some temperatures) is the enthalpy change associated with the process of forming the substance of interest starting from the separated components in the standard states of their most stable forms (temperature = T and pressure = 1 bar)

f HT

How can we calculate the enthalpy of formation of benzene at T = 298 K?

6 C (graphite, 298K, P ) + 3 H2 (ideal gas, 298K, P )

C6 H6 (liquid, 298K, P )

How can we calculate the enthalpy of formation of formaldehyde at T = 307 K?

C (graphite, 307K, P ) + H2 (ideal gas, 307K, P ) 1 + O2 (ideal gas, 307K, P ) 2 H2 CO(ideal gas, 307K, P )
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STANDARD THERMODYNAMIC FUNCTIONS

How can we calculate the enthalpy of formation of benzene at T = 298 K?

6 C (graphite, 298K, P ) + 3 H2 (ideal gas, 298K, P )

C6 H6 (liquid, 298K, P )

How can we calculate the enthalpy of formation of formaldehyde at T = 307 K?

C (graphite, 307K, P ) + H2 (ideal gas, 307K, P ) 1 + O2 (ideal gas, 307K, P ) 2

f HT

H2 CO(ideal gas, 307K, P )

=0

for each element in its reference form

f HT f HT f HT

=0 =0 =0

for graphite (at both 298 K and 307 K for H2 (at both 298 K and 307 K for O2 at 307 K
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STANDARD THERMODYNAMIC FUNCTIONS

Standard enthalpy of a reaction

aA1 + bA2 HT =
i

cA3 + dA4 =
i i f HT (Ai )

i Hm,T (Ai )

Reactants in standard states at temperature T

HT

Products in standard states at temperature T

f HT (reactants)
Elements in standard states at temperature T

f HT (products)

HT =

f HT (products)

f HT (reactants)
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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation

f HT

= + + + + +

f HT (step 1) f HT (step 2) f HT (step 3) f HT (step 4) f HT (step 5) f HT (step 6)

6 steps & use the properties of a state function

STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 1: Enthalpy change associated with the hypothetical transformation from an ideal gas at T and 1 bar to a real gas at T and 1 bar Need to calculate Hreal from Hideal

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb Hreal =

Hc
Ideal gas at T and P = 0 bar

H = Hideal

Ha +

Hb +

Hc
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STANDARD THERMODYNAMIC FUNCTIONS

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb Hreal = =V
T 0 P

Hc
Ideal gas at T and P = 0 bar

H = Hideal Ha H P

Ha + TV

Hb +

Hc

Ha =

(V

T V )dP
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STANDARD THERMODYNAMIC FUNCTIONS

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb Hreal =

Hc
Ideal gas at T and P = 0 bar

H = Hideal Hb = Ub = Ub + P Vb

Ha + Ub P

Hb +

Hc

Hb = 0
when

intermolecular interactions

check the behavior of real gases according to Boyles and Charles laws

Hb = 0
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STANDARD THERMODYNAMIC FUNCTIONS

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb Hreal = =V
T

Hc
Ideal gas at T and P = 0 bar

H = Hideal Hc H P

Ha + TV

Hb +

Hc

Hc =?
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STANDARD THERMODYNAMIC FUNCTIONS

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb Hreal = =V
T

Hc
Ideal gas at T and P = 0 bar

H = Hideal Hc H P

Ha + TV

Hb +

Hc

Hc = 0
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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 1: Enthalpy change associated with the hypothetical transformation from an ideal gas at T and 1 bar to a real gas at T and 1 bar Need to calculate Hreal from Hideal

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb
0 P

Hc
Ideal gas at T and P = 0 bar

H=

(V

T V )dP
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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 2: Enthalpy change associated with mixing the different substances at T and 1 bar (more important for gases)

CHAPTER 6

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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 3: Enthalpy change associated with bringing the substances from T and Po to T and P of interest

H (step3) =
i

Hi (T, P

T ,P )

Hi =

T T

CP,i dT +

P P

(Vi

T Vi

i )dP

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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 4: Enthalpy change associated with the reaction that leads to the formation of the compound of interest from the mixed elements at T and P.

Use of a calorimeter (see book for a description of how it works)

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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 5: Enthalpy change associated with bringing the substances from T and P at which they are formed to the standard conditions T and Po.

H (step5) =
i

Hi (T , P

T, P )

Hi =

T T

CP,i dT +

P P

(Vi

T Vi

i )dP

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STANDARD THERMODYNAMIC FUNCTIONS

How to determine the enthalpy of formation Step 6: Enthalpy change associated with the hypothetical transformation from a real gas at T and 1 bar to an ideal gas at T and 1 bar

Inverse process of step 1 (now done for the newly formed gas species)

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STANDARD THERMODYNAMIC FUNCTIONS

Relation between Ho and Uo

aA1 + bA2 H = U + PV

cA3 + dA4 H= V bVm,A2 U +P V

constant pressure

H = V = cVm,A3 + dVm,A4 V
i,gases
volume change of solids and liquids is small

U +P aVm,A1

i Vm,i

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STANDARD THERMODYNAMIC FUNCTIONS

Relation between Ho and Uo

aA1 + bA2 H = U + PV

cA3 + dA4 H= V bVm,A2 Vm,i = RT ng P RT = P

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constant pressure

U +P V

H = V = cVm,A3 + dVm,A4 V
i,gases i i,gases i Vm,i

U +P aVm,A1

ng

Vm,i

STANDARD THERMODYNAMIC FUNCTIONS

Relation between Ho and Uo

aA1 + bA2 H = U + PV

cA3 + dA4 H= V U +P V

constant pressure

H =

U +P

H = H U

U +

ng RT

if there are no gases

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STANDARD THERMODYNAMIC FUNCTIONS

Hesss law Often the reaction that forms a compound from its elements cannot be done.

2C (graphite) + 3H2 (g )
7 (1) C2 H6 (g ) + O2 (g ) 2

C2 H6 (g )

Ho cannot be determined directly

2CO2 (g ) + 3H2 O(l)

CO2 (g )

H1 H2 H3

(2) C (graphite) + O2 (g )
1 (3) H2 (g ) + O2 (g ) 2

H2 O(l)

2C (graphite) + 3H2 (g )

C2 H6 (g )

(1) + 2 (2) + 3 (3)

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STANDARD THERMODYNAMIC FUNCTIONS

Hesss law Often the reaction that forms a compound from its elements cannot be done.

2C (graphite) + 3H2 (g )
7 (1) C2 H6 (g ) + O2 (g ) 2

C2 H6 (g )

Ho cannot be determined directly

2CO2 (g ) + 3H2 O(l)

CO2 (g )

H1 H2 H3

(2) C (graphite) + O2 (g )
1 (3) H2 (g ) + O2 (g ) 2

H2 O(l)

H =

H1 + 2 H2 + 3 H3
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STANDARD THERMODYNAMIC FUNCTIONS

Temperature dependence of Ho We know Ho at T1 and we would like to know Ho at T2:

d H = dT

dHm,i i dT

d H =? dT

d H = dT

i CP,m,i i

CP

Kirchhoffs Law T2

HT2

HT1 =

T1

CP dT
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STANDARD THERMODYNAMIC FUNCTIONS

Temperature dependence of Ho Kirchhoffs Law T2

HT2

HT1 =

T1

CP dT

If T is small:

HT2

HT1

CP (T2

T1 )

Otherwise use Kirchhoffs law with:

CP,m = a + bT + cT + dT
2

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STANDARD THERMODYNAMIC FUNCTIONS

Conventional entropies A lot of bookkeeping... in the end we are interested in S (1) Choose an arbitrary value (=0) for entropy of each element in a chosen reference state (T=0, Po) (2) Tabulate S for any change from elements in the chosen reference state to the desired substance in a standard state

Entropy reference state Pure element in its stable condensed form (solid or liquid) at 1 bar in the limit T 0 K

Arbitrary definition

Sm,0 = lim Sm,T = 0

T 0
pure element in its stable condensed form
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STANDARD THERMODYNAMIC FUNCTIONS

How about So at T > 0 K?

S = ST
If there is a phase change...

S0 =

T 0

Cp dT T

S=
0

Tpc

Cp dT + T

Spc +

T Tpc

Cp dT T

How about the conventional entropy of a compound? Its complicated!

qrev S= T

a chemical reaction is an irreversible process!

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STANDARD THERMODYNAMIC FUNCTIONS

Third law of thermodynamics Measurements of G for several reactions led Nernst (1907) to postulate

lim

G T

=0
P

G T

=
P

G T

=
P

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STANDARD THERMODYNAMIC FUNCTIONS

Third law of thermodynamics Measurements of G for several reactions led Nernst (1907) to postulate

lim

G T

=0
P

G T

=
P

S lim S=0

G T

=
P

Important not true when the substances involved in the reaction are not in internal equilibrium e.g., supercritical liquids
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STANDARD THERMODYNAMIC FUNCTIONS

Third law of thermodynamics For any isothermal process that involves only substances in internal equilibrium, the entropy change goes to zero as T goes to zero

lim

S=0

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STANDARD THERMODYNAMIC FUNCTIONS

How to calculate conventional entropies

A+B
element element

C
compound

S =0 T =0
Tf us 0

S =0

S =0 S =?

S = Sm,T2 =

Cp,m (solid) dT + T

f us Hm

T2 Tf us

Cp,m (liquid) dT + . . . T
there may be other phase changes

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STANDARD THERMODYNAMIC FUNCTIONS

How to calculate conventional entropies
Tf us 0

S = Sm,T2 =

Cp,m (solid) dT + T

f us Hm

T2 Tf us

Cp,m (liquid) dT + . . . T

If gases are involved we need to calculate the entropy change associated to the hypothetical transformation from an ideal gas at P = 1 bar and T to a real gas at P = 1 bar and T

S (ideal, T, P )
Real gas at T and Po

S (real, T, P )
Ideal gas at T and Po

Sa
Real gas at T and P = 0 bar

T = constant

Sb

Sc
Ideal gas at T and P = 0 bar

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STANDARD THERMODYNAMIC FUNCTIONS

How to calculate conventional entropies

S (ideal, T, P )
Real gas at T and Po

S (real, T, P )
Ideal gas at T and Po

Sa
Real gas at T and P = 0 bar

T = constant

Sb

Sc
Ideal gas at T and P = 0 bar

S P

=
T

V T

For steps a and c

Sb = 0

In the limit T0, the entropy of ideal and real gases become equal (statistical mechanics, Chem 132)
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STANDARD THERMODYNAMIC FUNCTIONS

Standard enthalpy of reaction

ST =
i

i Sm,T,i

usually tabulated at T = 298 K

At different T,

ST2 =

ST1 +

T2 T1

CP dT + phase change contributions T

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STANDARD THERMODYNAMIC FUNCTIONS

Standard Gibbs energy of reaction

aA + bB
pure separated reactants in their standard states at T

cC + dD
pure separated products in their standard states at T

GT =
i

i Gm,T,i

GT =
i

f GT,i

f GT

f HT,i

f ST,i

enthalpies of formation

from So and 3rd law of thermodynamics

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