Chap.

5: Standard Thermodynamic Functions of Reaction

5.1: Standard State of Pure Substance 5.2: Standard Enthalpy of Reaction 5.3: Standard Enthalpy of Formation 5.4: Determination of Standard Enthalpies of Formation and Reaction 5.5: Temperature Dependence of Reaction Heats 5.7: Conventional Entropies and the Third Law 5.8: Standard Gibbs Energy of Reaction 5.10: Estimation of Thermodynamic Properties

5.1: Standard States of Pure Substance

Pure Solids or Pure Liquids

P: 1 bar T: At the temperature of interest Example: V m, 200

The molar volume of a pure solid or liquid at 1 bar and 200 K.

Pure Gas

P: 1 bar T: At the temperature of ideal gas Standard States of Solution: See chap. 9 & 10.

5.2: Standard Enthalpy of Reaction

HT Standard Enthalpy Change of Reaction,

The enthalpy change for the process of transforming stoichiometric numbers of moles of the pure, separated reactants, each in its standard state at temperature T, to stoichiometric numbers of moles of the pure, separated products, each in its standard state at temperature T. HT is also called the Heat of Reactionand labeled as r HT .

Example: aA + bB cC + dD HT is: The H T cH m,T C dH m,T D aH m,T A

bH m,T B

Recall the stoichiometric numbers, i

H T H m,T ,i i i

Example:

2C6H6(l) + 15O2(g) 12CO2(g) + 6H2O(l)

H T 12 H m,T CO 2 , g 6H m,T H 2O, l 2H m,T C6 H6 , l 15H m,T O2 , g

HT depends on how the reaction is Note:

written. Equ-5.4: 2H2(g) + O2(g) 2H2O(l) H298 572 kJ/mol Equ-5.5: H2(g) + O2(g) H2O(l) H298 286 kJ/mol

 Phase Abbreviations

s:

Solid state

l:
g:

Liquid state
Gas state

aq:
cr:

Aqueous solution
Crystalline solid

am:
cd: fl:

Amorphous solid
Condense state Fluid phase (liquid or gas)

5.3: Standard Enthalpy of Formation

The Standard Enthalpy of Formation, f H T ,

(standard heat of formation) of a pure substance at temperature T is H for the process in which one mole of the substance in its standard state at T is formed from the corresponding separated elements at T, each element being in its reference form. The Reference From (reference phase) of an element at temperature T is usually taken as the form of the element that is most stable at T and 1-bar pressure.

 See the example of H2CO on p. 142.

For an element in its reference form, f H T

T i

f H

T ,i

See Fig-5.1 on p. 143

Reactants aA + bB in their standard states at T

(1)

Products cC + dD in their standard states at T

(2)
Elements in their standard states at T

(3)

Note: H is a state function

H 1 H 2 H 3
H T H T i

H 2

H 3
0 b f H T , B a f H T , A b f H T , B d f H T , D a f H T , A b f H T , B c f H T ,C d f H T , D

0 a f H T , A c f H T ,C

H 1

f H T ,i i

5.4: Determination of Standard Enthalpies of Formation and Reaction

1. Measurement of fH: 6 steps on p. 143 144.
1) For gaseous components:

Ideal gas at T, 1 bar Real gas at T, 1 bar 2) Measure H for mixing the pure element at T and 1 bar. 2 2 CP dT 1 V TV dP to bring the 3) Use H 1 mixture from T and 1 bar to the real reaction conditions.

4) Use a calorimeter to measure H for the reaction in which the compound is formed from the mixed elements. (Experiment!)
5) Find H for bringing the products from the real reaction conditions to T and 1 bar. Use
H CP dT 1
2 2 1

V TV

dP

(Equ-4.63*)

6) If compound i is a gas, we calculate H for the hypothetical transformation of i from a real gas to an ideal gas at T and 1 bar.

Example 5.1: see p. 144

Find H 298 for the combustion of one moles of the simplest amino acid, glycine, NH2CH2COOH, according to

Solution:
H 298 i

9 NH 2CH 2COOH( s) O2 ( g ) 4

5 1 2CO 2 ( g ) H 2O(l ) N2 ( g ) 2 2

f H

298

H 298

9 5 1 ( 528.10) 0 2( 393.509) ( 285.830) 0 4 2 2 973.49kJ / mol

2. Calorimetry 1) Constant-V calorimeter: Fig-5.4 on p. 145

2) Constant-P calorimeter
3) Standard enthalpy of combustion, cHT:

The HT for the reaction in which one mole of the substance is burned in O2. Example 5.2: p. 146 Combustion of 2.016 g of solid glucose, C6H12O6 at 25 C in an adiabatic bomb calorimeter with heat capacity 9550 J/K gives a temperature rise of 3.282 C. Find cU298 of glucose.

U = CvT = (-9550 J/K) 3.282K = -31.34 kJ nglucose = 2.016g / 180.16 g/mol = 0.01119 mol cU298 = -31.34 kJ / 0.01119 mol = -2801 kJ/mol
3. Relations between H and U

H = (U + PV) = U + PV For an ideal gas, PV = nRT, thus, HT = UT + nRT

Example 5.3: p. 147

Calculation of fU from fH

4. Hesss Law: See p. 147 148.

5. Calculation of Hideal - Hreal

Generate a hypothetical isothermal at T

Real gas at P (a) Ideal gas at P (c)

(b) Real gas at 0 bar Ideal gas at 0 bar

H Ha Hb Hc H

H ideal T , P H real T ,0 bar 0 0 H ideal T , P

H real T , P H real T , P

Ha
0 P

Hb

Hc

V TV dP

H real T , P

P 0

V T

V dP
P

Intermolecular forces make Ureal and Hreal slightly less than Uideal and Hideal at 1 bar. Conventional Enthalpy: H
m,298

=0

5.5: Temperature Dependence of Reaction Heats

Question:

If H at T1, how could we get H at T2?

H d dT d H dT
i i i iH m ,i

d dT
dH m ,i

d dT
i

H m ,i i i

C P ,m.i dT
i

dT

dT

i i

C P , m ,i

Note : dH

C P dT
C P , m ,i i CP

dT d H Because dT
T2 T1

d H dT

d H pr

H re

dH pr dT

dH dT

re

C Cre pr

CP

CP P

d H H H
T1 T2 T2 T1

C P dT

d H

T2 T1

C dT
T2

T1

T2 T1

C P dT C P , m ,i i i

Kirchoff' s Law : H

C P dT , C P

1. Over a short temperature range, C P is approximat ely a constant. Thus H T2 H T1 C P T2 T1 .

2. If T T2 T1 is large, we let C P T

a bT

cT 2

Where a, b, c,

, are determined by experiment s.

 Example 5.5: p. 152

Use Appendix data and the approximation that CP is independent of T to estimate H1200 for the reaction: 2CO(g) + O2(g) 2CO2(g) Solution: Use Kirchhoffs Law
CP i CP C P , m ,i i

2 29.116

29.355 2 37.11

-13.37 J/mol K H
298 1200 298 C P dT H 298 C P T2 T1

1200

H1200 H1200

565.968 578.03 kJ

13.37 1200 298

 Example 5.6: See p. 152 - 153

CP i i C P , m ,i 2C P ,m ,CO C P ,m ,O2 C P ,m ,CO 2

b T

c T2

d T3

a b c c d d
H T2 H 1200

2aCO 2bCO 2cCO 2d CO

aO2 bO2 cO2 d O2

2aCO 2 2bCO 2 2cCO 2 2d CO 2

-2 28.74 - 25.67 2 21.64

39.87 J/mol K 0.11744 J/mol K 2

-2 - 0.00179 - 0.01330 2 0.06358 -2 1.046 10 -5 - - 3.764 10 -6

2 - 4.057 10 -5 2 9.700 10 -9

9.8296 10 5 J/mol K 3 -2 - 4.288 10 -9 - - 7.310 10 -11 2.8049 10 8 J/mol K 4

H T1

H 1200

1 1 1 b T22 T12 c T23 T13 d T24 T14 2 3 4 1 565968 - 39.87 901.85 0.11744 1.3511 10 6 2 1 1 9.8296 10 5 1.7015 109 2.8049 10 8 2.0657 1012 3 4 563.85 kJ/mol a T2 T1

5.7: Conventional Entropy and the Third Law

1. The reference state of entropy:

The pure element in its stable condensed form at 1 bar in the limit T 0 K. See Equ-5.22*.
S
m,0

lim S
T 0

m ,T

0 for element in stable condensed form

To find the convention al S m,T for an element at any T , use

T2 T1

CP dT T

2. The 3rd law of thermodynamics

Nernst in 1907: lim

T

G T

0
P

Equ - 5.23

In Equ-4.51:
lim S
T 0

G T

S
P

Equ-5.23 implies that

Nernst-Simon Statement of the 3rd 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
T 0

3. Determination of Conventional Entropies

Example:

H2(g) + O2(g) H2O(l)

S
T

m ,i

1 S
T 0

m, H 2

1 S m ,O2 1 S m , H 2O 2
0 , lim S m , H 2O T 0

lim S m , H 2 0

0 , lim S m ,O2

This means S 0

0 for a perfect crystallin e solid.

T2

CP Let T1 0 : ST2 ST1 ST2 S 0 ST2 dT 0 T Note : we usually need to think about phase changes
S m ,T2 T fus 0 C P ,m ( s )

dT

Hm fus

Tvap T fus

C P ,m (l )

T fus
P 0

T
Vm T

dT

Hm vap

T2 Tvap

C P ,m ( g )

Tvap

dT

In addition, we need to think about the differences between real gas and ideal gas : S
m ,id

m , re

R dP P

Example 5.7: See p. 159 160.

4. Standard Entropy of Reaction

S S

T i T2

m ,T ,i

, because C dT T
P

Si T

C P ,i
P

T1

T2 T1

Example 5.8: See p. 161

Use data in the Appendix to find S298 for the reaction: 4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l) S298 = -4(192.45) 3(205.138) + 2(191.61) + 6(69.91) = -582.53 kJ/molK

5.8: Standard Gibbs Energy of Reaction

GT The Standard Gibbs Energy: i Gm ,T ,i i

If the reaction is one of formation of a substance from its elements in their reference forms, then GT is the standard Gibbs energy of formation fGT of the substance.
GT i i GT ,i where f GT ,i f H T ,i T f ST , i f

Review knowledge of General Chem II: Example 5.9: See p, 162 Example 5.10: See p. 162

5.10: Estimation of Thermodynamic Properties Bond Additivity: See Fig-5.13 on p. 165. Bond Energies: The idea of average bond energy. Group Additivity: Sign of G: Entropy of gases are substantially higher than condense states. Substances with molecules of similar size have similar entropies. Other Estimation Methods: Chaps 19 & 21.