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## PowerPoint Slideshow about 'Thermodynamics' - rune

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### Thermodynamics

Part 2

Free Energy

- DG - Gibbs free energy - maximum possible useful work at constant T and P
- DG = DH – TDS
- Our predictive tool for reactions
DG > 0 non-spontaneous

DG = 0 at equilibrium

DG < 0 spontaneous

- For a spontaneous process:
maximize entropy minimize energy

Standard molar free energy of formation - DGof

DGof = 0 for free elements in standard state

Calculate free energy change for a reaction

CaCO3 (s) CaO (s) + CO2 (g)

DGof :

-1129 kJ/mole

-604 kJ/mole

-394 kJ/mole

Is this a spontaneous reaction?

DG = DH – TDS

CH4 (g) C (diamond) + 2H2 (g)

Calculate DHorxn, DSorxn, and DGorxn

DG = DH-TDS

Can the reaction become spontaneous?

DG = 0 = DH - TDS

Teq = DH/DS

(estimate)

Can it rain diamonds on Neptune and Uranus?

Neptune/Uranus

blue color – CH4

10-50GPa

2000-3000K

C (graphite) + O2 (g) CO2 (g) DH1

C (graphite) + ½ O2 (g) CO (g) DH2

Can't run this reaction, you get CO and CO2

CO (g) + ½ O2 (g) CO2 (g) DH3

Reactions are additive!

C (graphite) + O2 (g) CO2 (g) DH1

CO (g) + ½ O2 (g) CO2 (g) DH3

C (graphite) + O2 (g) CO2 (g) DH1

CO2 (g) CO (g) + ½ O2 (g) -DH3

C (graphite) + ½ O2 (g) CO (g) DH2 = DH1-DH3

Biological pathways

Important in the metabolism of glucose

Glucose + 6O2 CO2 + H2O

First step in glycolytic pathway:

Glucose + HPO4-2 + H+ [glucose-6-phosphate]- + H2O

DGo’ = 13.8 kJ

Is this reaction spontaneous?

Coupled reactions

Glucose + HPO4-2 + H+ [glucose-6-phosphate]- + H2O

DGo’ = 13.8 kJ

ATP-4 + H2O ADP-3 + HPO4-2 + H+

DGo’ = -30.5 kJ

Glucose + ATP-4 [glucose-6-phosphate]- + ADP-3

DGo’ = 13.8 + -30.5 = -16.7 kJ

the equilibrium constant

DGo = -2.303RTlog K

T - kelvin temperature

R - gas constant – 8.314 J/K-mole

- DGo > 0 K < 1 reactant favored
- DGo = 0 K = 1
- DGo < 0 K > 1 product favored

log K = DGorxn x 1000

-2.303 x 8.314 J/K-mole x 298 K

Diamonds are NOT forever!Cdiamond Cgraphite

DGof :

3 kJ/mole

0

DGorxn = 0 – 3 = -3 kJ

log K = 0.53 K = 100.53 = 3.4

very very very very slow kinetics

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