Thermodynamics of Dissipative Self-Assembly Ger Koper - - PowerPoint PPT Presentation

▶
thermodynamics of dissipative self assembly
SMART_READER_LITE
LIVE PREVIEW

Thermodynamics of Dissipative Self-Assembly Ger Koper - - PowerPoint PPT Presentation

Dec 02, 2023 523 likes •717 views

Thermodynamics of Dissipative Self-Assembly Ger Koper DelftChemTech Co-workers TU Delft / ChemE NTNU Jan van Esch Dick Bedeaux Rienk Eelkema Signe Kjelstrup Job Boekhoven (now at NU) Universitat de Barcelona Wouter Hendriksen

slide-1
SLIDE 1

DelftChemTech

Thermodynamics

  • f

Dissipative Self-Assembly

Ger Koper

slide-2
SLIDE 2

20 August 2012 2

Co-workers

TU Delft / ChemE

Jan van Esch Rienk Eelkema Job Boekhoven (now at NU) Wouter Hendriksen Christophe Minkenberg

TU/ e

Luc Brunsveld Ralph Bosmans

NTNU

Dick Bedeaux Signe Kjelstrup

Universitat de Barcelona

Miguel Rubí Ignacio Pagonabarraga

slide-3
SLIDE 3

20 August 2012 3

Classical Self Assembly

Law of mass action mic K ⎯⎯⎯⎯ → ←⎯⎯⎯ ⎯

1 2 3

xt/xc

1 2 3

x1/xc xN/xc

slide-4
SLIDE 4

20 August 2012 4

Classical Self Assembly

Equilibrium mic K ⎯⎯⎯⎯ → ←⎯⎯⎯ ⎯

0.2 0.4 0.6 0.8 1

conversion ξ

  • 1.6
  • 1.2
  • 0.8
  • 0.4

ΔG/(RT)

slide-5
SLIDE 5

20 August 2012 5

Classical Self Assembly

Spontaneous

mic K ⎯⎯⎯⎯ → ←⎯⎯⎯ ⎯

1 2 3

xt/xc

1 2 3 1 2 3

xt/xc

  • 1.6
  • 1.2
  • 0.8
  • 0.4

ΔG/(RT) x1/xc xN/xc

G Δ <

slide-6
SLIDE 6

20 August 2012 6

Controlled Self Assembly

mic K ⎯⎯⎯⎯ → ←⎯⎯⎯ ⎯ K ⎯⎯→ ←⎯⎯

slide-7
SLIDE 7

20 August 2012 7

Example 1: micelles

55

A

5

A

slide-8
SLIDE 8

20 August 2012 8

Example 2: responsive vesicles

77

A

7

A

slide-9
SLIDE 9

20 August 2012 9

Enhanced Control of Self Assembly

mic K ⎯⎯⎯⎯ → ←⎯⎯⎯ ⎯

f

k

b

k

slide-10
SLIDE 10

20 August 2012 10

Required work: driving reactions

forwardG

Δ

micG

Δ

backwardG

Δ

backward-driveG

Δ

forward-driveG

Δ

tot drive f,b

G G Δ = Δ

∑

slide-11
SLIDE 11

20 August 2012 11

Example: gelation

M e t h y l a t i

  • n

Gelation Hydrolysis

dibenzoyl-(l)-cystine

slide-12
SLIDE 12

20 August 2012 12

Transient gelation

slide-13
SLIDE 13

20 August 2012 13

Thermodynamic Analysis

methG

Δ

gelG

Δ

hydrG

Δ

backward-driveG

Δ

forward-driveG

Δ

slide-14
SLIDE 14

20 August 2012 14

Driving Reactions

  • Methylation:

DMS + H2 O → MMS- + MeOH + H+

  • Hydrolysis:

H+ + OH- → H2 O

  • Net reaction:

DMS + OH- → MMS- + MeOH Gibbs energy change of reaction

398.4 kJ/mol

  • rG

Δ = −

slide-15
SLIDE 15

20 August 2012 15

Efficiency of Driving Reactions

  • Methylation reaction
  • Hydrolysis

Efficiency of free energy transfer

meth

10 kJ/mol

  • G

Δ ≈

hydr meth

10 kJ/mol

  • G

G Δ = −Δ ≈ − 3% ε ≈

slide-16
SLIDE 16

20 August 2012 16

Thermodynamic Analysis

  • Stationary operation
  • Methylation/hydrolysis rate:
  • Gibbs energy change of reaction
  • Lost work
  • Entropy production

398.4 kJ/mol

  • rG

Δ = −

lost

20 kJ/(L hr) 5.6 W/L

  • r

W r G = − Δ ≈ ≈

  • 50 mM/hr

r =

  • lost

amb

0.02 J/(K L) W S T = ≈

slide-17
SLIDE 17

20 August 2012 17

Conclusions

  • Self-assembling systems
  • respond faster when driven
  • are dissipative when driven by irreversible reactions
  • can be used to store energy !