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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

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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

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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?

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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

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2D spectra correlate excited and detected frequencies 5 Early waiting times Excitation Detection

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Later waiting times 6 Excitation Detection Excitation Detection 2D spectra correlate excited and detected frequencies

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Frequency Frequency Correlation Function (FFCF) 7 Frequency Correlation Waiting time (ps) C(t) Excitation Detection Excitation Detection How fast?

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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)

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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

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Linear Polymer Crowders 10 guar Linear Polymer Frequency (cm -1 ) 1972 cm -1 Probe mannose Control monomer [Ru(CO) 3 Cl] 2 (-Cl) 2

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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

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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

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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

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Collective hydration Credit: John King Guar experiences collective hydration 14 guar Independent hydration mannose Independent hydration Mannose experiences independent hydration

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What is the Role of Polymer Shape? 15 guar Ficoll How are hydration dynamics affected by branched polymers? Inspiration: Gruebele Group

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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

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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.

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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

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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)

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20 Molecular interactions in concentrated polymer solutions represent a frontier in scientific inquiry Independent hydration Collective hydration Summary and Outlook

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Acknowledgements 21 Kevin Kubarych John King Josef Dunbar Aaron White Evan Arthur Laura Kiefer Peter Eckert Ved Roy

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Why we do not use H2O 22

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Background Free 23 conservation of momentum dictates that all wave vectors must add up to zero.

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