Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy ISMS...
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Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy ISMS 17 June 2014 Kimberly R. Daley, John T. King, Kevin J. Kubarcyh University of Michigan
Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy ISMS 17 June 2014 Kimberly R. Daley, John T. King, Kevin
Dynamics of Model Hydraulic Fracturing Liquid Studied by
Two-Dimensional Infrared Spectroscopy ISMS 17 June 2014 Kimberly R.
Daley, John T. King, Kevin J. Kubarcyh University of Michigan
Slide 2
Complexity and Heterogeneity 2 2DIR: observe solvent and
hydration dynamics on a picosecond timescale J. Phys. Chem. B 116
(2012) 5604 J. Am. Chem. Soc. 134 (2012) 18705 J. Chem. Phys. 138
(2013) 144501 J. Phys. Chem. B 117 (2013) 15407 Phys. Rev. Lett.
108 (2012) 157401 Hydration Dynamics Heterogeneous mixtures Systems
studied The fundamental properties of heterogeneous polymer
mixtures remains unexplored by modern multidimensional
spectroscopy
Slide 3
3
http://www.propublica.org/special/hydraulic-fracturing-national
High Pressure Variable Temperature Inspiration: Hydraulic
Fracturing Liquids = sand = guar = water Why study hydraulic
fracturing liquid? What can we learn that correlates hydration
properties to polymer properties? How do heterogeneous mixtures
make a difference?
Slide 4
Two-Dimensional Infrared Spectroscopy (2DIR) 4 Example 2DIR
Spectrum Excitation Frequency Detection Frequency Tracks probe
solute Extracts information about solvent- solute interactions J.
M. Anna, C. R. Baiz, M. R. Ross, R. McCanne, K. J. Kubarych, Int.
Rev. Phys. Chem. 2012, 31, 367-419 Excitation Detection CORM-2 in D
2 O
Slide 5
2D spectra correlate excited and detected frequencies 5 Early
waiting times Excitation Detection
Slide 6
Later waiting times 6 Excitation Detection Excitation Detection
2D spectra correlate excited and detected frequencies
Slide 7
Frequency Frequency Correlation Function (FFCF) 7 Frequency
Correlation Waiting time (ps) C(t) Excitation Detection Excitation
Detection How fast?
Slide 8
Analyzing FFCF for Hydration Dynamics 8 Frequency Correlation
Time (ps) C(t) Time (ps) 1. Correlation functions for different
concentrations 2. Fit each C(t) to determine decay time (hydration
dynamics) Concentration Hydration dynamics 3. Graph each decay with
its respective concentration Hydration Dynamics: Chemical
information describing the molecular motion of solvent surrounding
the probe. Decay of the correlation function Waiting time (ps)
Slide 9
Question 2: How does polymer shape affect solvation dynamics of
heterogeneous mixtures? Question 1: How are solvent dynamics
affected by the connectivity of the monomer units? Building Model
Hydraulic Fracturing Liquid 9 Probe the dynamics of polymers and
monomers mixtures Study the dynamics of a probe as a function of
increasing polymer concentration
Slide 10
Linear Polymer Crowders 10 guar Linear Polymer Frequency (cm -1
) 1972 cm -1 Probe mannose Control monomer [Ru(CO) 3 Cl] 2 (-Cl)
2
Slide 11
Hydration Dynamics Concentration (mg/mL) guar Guar experiences
a dynamical transition in dynamics 11 C(t) waiting time (ps) 1.7
mg/ml 6.2 mg/ml 14.0 mg/ml 26.2 mg/ml 28.7 mg/ml Hydration Dynamics
(ps) Concentration (mg/mL) guar Linear polymer Excitation Detection
Excitation Detection concentration
Slide 12
C(t) waiting time (ps) Mannose experiences little change in
dynamics 12 guar mannose Hydration Dynamics (ps) Concentration
(mg/mL) Control monomer Excitation Detection Excitation
Detection
Slide 13
Different hydration dynamics in the same concentration range 13
Concentration (mg/mL) Hydration Dynamics (ps) guar mannose Time
(ps) C(t) Time (ps) Waiting time (ps) Collective Independent
Slide 14
Collective hydration Credit: John King Guar experiences
collective hydration 14 guar Independent hydration mannose
Independent hydration Mannose experiences independent
hydration
Slide 15
What is the Role of Polymer Shape? 15 guar Ficoll How are
hydration dynamics affected by branched polymers? Inspiration:
Gruebele Group
Slide 16
Branched Polymer Crowders 16 Ficoll Branched Polymer Sucrose
Radius < 0.5 nm Ficoll 400 Radius 15-30 nm Ficoll 70 Radius 2-7
nm ~same size of representative protein sucrose Control
monomer
Slide 17
Ficoll experiences the same hydration dynamics as sucrose 17
Time (ps) C(t) Time (ps) Waiting time (ps) Collective Independent
King, J. T.; Arthur, E. J.; Brooks, C. L.; Kubarych, K. J.JACS
2014, 136, 188-94.
Slide 18
18 What is the Role of Probe? Frequency (cm -1 ) 1972 cm -1
Neutral [Re(CO) 3 (H 2 O) 3 ]Br Cationic Frequency (cm -1 ) [Ru(CO)
3 Cl] 2 (-Cl) 2
Slide 19
19 Re(H20) 3 (CO) 3 + Br - senses similar dynamics as [Ru(CO) 3
Cl] 2 (-Cl) 2 Excitation Detection Excitation Detection Preliminary
data of Re(H20) 3 (CO) 3 + Br - C(t) waiting time (ps)
Slide 20
20 Molecular interactions in concentrated polymer solutions
represent a frontier in scientific inquiry Independent hydration
Collective hydration Summary and Outlook
Slide 21
Acknowledgements 21 Kevin Kubarych John King Josef Dunbar Aaron
White Evan Arthur Laura Kiefer Peter Eckert Ved Roy
Slide 22
Why we do not use H2O 22
Slide 23
Background Free 23 conservation of momentum dictates that all
wave vectors must add up to zero.