Crystal Nucleation and Crystal Growth and Mass Transfer in Internally

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Crystal Nucleation & Crystal Growth and Mass Transfer in Internally Mixed Sucrose/NaNO3 Particles Zhi-Ru Ji, Yun Zhang, Shu-Feng Pang, and Yun-Hong Zhang J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b08004 • Publication Date (Web): 27 Sep 2017 Downloaded from http://pubs.acs.org on October 1, 2017

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The Journal of Physical Chemistry

1

Crystal Nucleation & Crystal Growth and Mass Transfer in

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Internally Mixed Sucrose/NaNO3 Particles

3

Zhi-Ru Ji, Yun Zhang, Shu-Feng Pang, Yun-Hong Zhang∗

4

The Institute of Chemical Physics, School of Chemistry and Chemical Engineering, Beijing

5

Institute of Technology. Beijing 100081, People’s Republic of China

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

∗

Email: [email protected]

Phone:86-10-68913596

Fax:86-10-68913596 1

ACS Paragon Plus Environment


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ABSTRACT:

23

Secondary organic aerosols (SOA) can exist in a glassy or semi-solid state under

24

low relative humidity (RH) conditions, in which the particles show non-equilibrium

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kinetic characteristics with changing ambient RH. Here, we selected internally mixed

26

sucrose/NaNO3 droplets with organic to inorganic molar ratio (OIR) of 1:8, 1:4, 1:2

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and 1:1 as a proxy for multicomponent ambient aerosols to study crystal nucleation &

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growth process and water transport under highly viscous state with the combination of

29

a RH controlling system and a vacuum Fourier transform infrared (FTIR)

30

spectrometer. The initial efflorescence RH (ERH) of NaNO3 decreased from ~45% for

31

pure NaNO3 droplets to ~38.6% and ~37.9 % for the 1:8 and 1:4 sucrose/NaNO3

32

droplets, respectively. While no crystallization of NaNO3 occurred for the 1:2 and 1:1

33

droplets in the whole RH range. Thus, the addition of sucrose delayed the ERH and

34

even completely inhibited nucleation of NaNO3 in the mixed droplets. In addition, the

35

crystal growth of NaNO3 was suppressed in the 1:4 and 1:8 droplets most likely due

36

to the slow diffusion of Na+ and NO -3 ions at low RH. Water uptake/release of

37

sucrose/NaNO3 particles quickly arrived at equilibrium at high RH, while the

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hygroscopic process was kinetically controlled under low RH. The half-time ratio

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between the liquid water content and the RH was used to describe the mass transfer

40

behavior. For the 1:1 droplets, no mass limitation was observed with the ratio

41

approached to 1 when RH was higher 53%. The ratio raised one order of magnitude

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under ultra-viscous state within RH from 53% to 15%, and increased further one order

43

of magnitude at RH

354

53% in sub-second time resolution. However, when the RH is below ∼53%, the

355

humidiﬁcation and dehumidiﬁcation curves are not merged, suggesting the hysteresis

356

in water uptake/release. Similar hygroscopicity curve with pulsed RH changes is

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estimated in the Supporting Information (Figures S4) for 1:2 sucrose/NaNO3 droplets.

358

To more fully understand the water transfer limitation in ternary particles of

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sucrose/sodium nitrate/water, we quantitatively analyze the ratio of half-time between

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the liquid water content and the RH during water uptake and loss on 1:1 and 1:2

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sucrose/NaNO3 mixtures. In the experiment, the ambient RH is kept constant at 60%

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for 30 minutes to keep droplets balance with gas phase. Then the RH decreases and

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increases by step-wise. And at 53% < RH < 80%, the RH is controlled by applying the

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rapid scan mode and the pulsed RH change method, which allow us to capture the

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information of mass transfer with sub-second time resolution.

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Figure 5 gives the RH dependence of the ratio of the half-time for 1:1

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sucrose/NaNO3 mixture. When the final RH values are above 53%, the ratios keep

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values around about 1, indicating free water transport in condensed phase and in gas

369

phase. However, the ratio raised one order of magnitude under ultra-viscous state

370

within RH from 53% to 15%. And when both the initial and the final RHs are below

371

15%, the half-time ratio increases one order of magnitude further, indicating the much 17



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slower changing rate of liquid water for glassy aerosols. It is clear that there are

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different characteristics of mass transfer inhibition for ultra-viscous aerosols and for

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glassy aerosols. Similar ratios of the half-time are estimated in the Supporting

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Information (Figures S5) for 1:2 sucrose/NaNO3 aerosols.

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Estimating a timescale for droplets to adapt to a change in ambient humidity

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would be greatly helpful for qualitatively assessing the change in rate of mass transfer.

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In this study, we use the characteristic relaxation timescale (τ), i.e., e-folding time of

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equilibration in aerosol, to represent the kinetics of mass transport. In each step, τ for

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condensation or evaporation of water from viscous droplets following a rapid RH

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change can be described by the Kohlrausch–Williams–Watts (KWW) function which

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is a stretched exponential function.49,50 The response function, F(t), responding to an

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applied perturbation over time, t, can be expressed as:51 F (t ) ≈ exp  −(t / τ)β 

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(5)

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where β is a fitting parameter and decreases markedly as the system approaches a

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glass

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expressed as:19

388

transition.50 The response function for a change in liquid water content is

F (t ) ≈

A(t ) − A(∞) A(0) − A(∞)

(6)

389

where A(t) is the liquid water band area of aerosol at time t, A(0) and A(∞)

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correspond to the initial and eventual value of the liquid water band area, respectively.

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Eq. (5) and (6) can be combined to give:

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A(t ) ≈ A(∞) + ( A(0) − A(∞)) exp  −(t / τ)β 

(7)

18


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A direct analysis of the kinetic profiles is well-described by eq. (7). Through

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KWW fitting, τ can be obtained. An example of KWW fitting in the RH step from 30%

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to 24% has been shown in Figure S6 in the Supporting Information.

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Figure 6 gives the characteristic relaxation timescale (τ) of pure sucrose droplets

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and 1:1, 1:2 sucrose/NaNO3 mixtures. Compared with pure sucrose droplets, the

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addition of NaNO3 slightly decreases the timescale for mass transfer with the

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surrounding vapor and accelerates the release of water at the similar RH ranges.

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Sucrose is typical a soluble organic chemical with many hydroxyl groups which is

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able to form strong hydrogen bonds with water moleculues.21 Thus, the faster

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diffusional kinetics of water in a sucrose/NaNO3 particle reflects the impact that the

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addition of NaNO3 has on the hydrogen bonding network in the aqueous sucrose

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droplets, leading to significant changes in the viscosity of the sucrose matrix.

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4. Conclusions

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Throughout the whole study, we found that the addition of sucrose decreased the

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mass growth factor of the mixed aerosols when compared with the pure NaNO3.

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Moreover, the initial ERH of NaNO3 decreased from ~45% for pure NaNO3 droplets

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to ~38.6% and ~37.9 % for the 1:8 and 1:4 sucrose/NaNO3 droplets, respectively. And

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no crystallization of NaNO3 occurred for the 1:2 and 1:1 droplets in the whole RH

411

range. A possible explanation is that sucrose molecules suppressed the formation of

412

contact ion pairs between Na+ and NO-3 , which delayed the nucleation of NaNO3 in

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the mixed sucrose/NaNO3 droplets. The kinetic limitation for the diffusion of Na+ and

414

NO-3 ions onto the NaNO3 crystal seeds slowed the crystal growth of NaNO3 at low 19



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RH in 1:8 and 1:4 sucrose/NaNO3 droplets. Therefore, in highly viscous amorphous

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aerosols, the crystal growth of NaNO3 cannot be neglected at low RH. Water

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uptake/release of sucrose/NaNO3 particles quickly arrived at equilibrium at high RH,

418

while the hygroscopic process was kinetically controlled under low RH. Here, it was

419

found that water transfer limitation existed in 1:1 sucrose/NaNO3 droplets in RH

420

pulses with RH ＜ 53% and there were different characteristics of mass transfer

421

inhibition for ultra-viscous aerosols and for glassy aerosols. Besides, water transfer

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limitation was decreased with increasing NaNO3 mole fraction for the mixed

423

sucrose/NaNO3 droplets by 1:1 and 1:2. This is likely due to the fact that sodium

424

nitrate breaks hydrogen bonds between sucrose and water, which can affect the

425

viscosity of the sucrose matrix. Understanding the nucleation and crystallization

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processes and water transport to and from highly viscous and glassy droplets is an

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imperative step toward studying the influence of highly viscous and glassy aerosols

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on the Earth’s atmosphere and cloud formation.

429

Supporting Information

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The Supporting Information includes a schematic of the instrument, two figures of the

431

infrared spectra in the dehumidifying processes and the liquid water content for mixed

432

sucrose/NaNO3 particles with OIR of 1:8 and 1:2. The hygroscopicity curve with

433

pulsed RH changes and the half-time ratio for 1:2 sucrose/NaNO3 particles are also

434

given. Besides, a KWW fitting result of 1:1 sucrose/NaNO3 droplets in the RH step

435

from 30% to 24% is included.

436

Corresponding Authors 20


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* Corresponding author telephone: 86-10-68913596. E-mail: [email protected].

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Acknowledgment

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We gratefully appreciate financial support from the National Natural Science

440

Foundation of China (Nos. 91544223, 41175119, 21473009, and 21373026) and the

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Ministry of Science and Technology of China (No.2016YFC0203000). The authors

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wish to express their gratitude to the anonymous reviewers for the stimulating

443

suggestions and discussions.

444

References

445

(1) Haywood, J.; Boucher, O., Estimates of the direct and indirect radiative forcing due to

446

tropospheric aerosols: A review. Reviews of Geophysics 2000, 38 (4), 513–543.

447

(2) Yu, Y.; Kaufman, M.; Chin, G.; Feingold, L.; Remer, T.; Anderson, Y.; Balkanski, N.;

448

Bellouin, O.; Boucher, S.; Christopher, P., H. review of measurement-based assessments of

449

the aerosol direct radiative effect and forcing, Atmos. Chem. Phys. (6). Physical Review D

450

Particles Fields 2006, 83 (5), 501-514.

451

(3) Tang, M.; Larish, W. A.; Fang, Y.; Gankanda, A.; Grassian, V. H., Heterogeneous

452

Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

453

The Journal of Physical Chemistry A 2016, 120 (28), 5609-5616.

454

(4) Lohmann, U.; Feichter, J., Global indirect aerosol effects: a review. Atmospheric

455

Chemistry & Physics 2005, 5 (3), 715-737.

456

(5) Pósfai, M.; Buseck, P. R., Nature and Climate Effects of Individual Tropospheric Aerosol

457

Particles. Annual Review of Earth & Planetary Sciences 2010, 38 (1), 17-43.

458

(6) Rubasinghege, G.; Elzey, S.; Baltrusaitis, J.; Jayaweera, P. M.; Grassian, V. H., 21



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 35

459

Reactions on Atmospheric Dust Particles: Surface Photochemistry and Size-Dependent

460

Nanoscale Redox Chemistry. Journal of Physical Chemistry Letters 2010, 1 (11), 1729-1737.

461

(7) Chan, M. N.; Chan, C. K., Hygroscopic properties of two model humic-like substances

462

and their mixtures with inorganics of atmospheric importance. Environmental science &

463

technology 2015, 37 (22), 5109-15.

464

(8) Shiraiwa, M.; Ammann, M.; Koop, T.; Poschl, U., Gas uptake and chemical aging of

465

semisolid organic aerosol particles. Proceedings of the National Academy of Sciences of the

466

United States of America 2011, 108 (27), 11003-8.

467

(9) Docherty, K. S.; Stone, E. A.; Ulbrich, I. M.; Decarlo, P. F.; Snyder, D. C.; Schauer, J. J.;

468

Peltier, R. E.; Weber, R. J.; Murphy, S. M.; Seinfeld, J. H., Apportionment of Primary and

469

Secondary Organic Aerosols in Southern California during the 2005 Study of Organic Aerosols

470

in Riverside (SOAR-1). Environmental science & technology 2008, 42 (20), 7655-62.

471

(10) Price, H. C.; Murray, B. J.; Mattsson, J.; O'Sullivan, D.; Wilson, T. W.; Baustian, K. J.;

472

Benning, L. G., Quantifying water diffusion in high-viscosity and glassy aqueous solutions

473

using a Raman isotope tracer method. Atmospheric Chemistry and Physics 2014, 14 (8),

474

3817-3830.

475

(11) Roth, C. M.; Goss, K. U.; Schwarzenbach, R. P., Sorption of a diverse set of organic

476

vapors to urban aerosols. Environmental science & technology 2005, 39 (17), 6638-43.

477

(12) Virtanen, A.; Joutsensaari, J.; Koop, T.; Kannosto, J.; Yli-Pirila, P.; Leskinen, J.; Makela, J.

478

M.; Holopainen, J. K.; Poschl, U.; Kulmala, M.; Worsnop, D. R.; Laaksonen, A., An amorphous

479

solid state of biogenic secondary organic aerosol particles. Nature 2010, 467 (7317), 824-7.

480

(13) Debenedetti, P. G.; Stillinger, F. H., Supercooled liquids and the glass transition. Nature 22


Page 23 of 35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


481

2001, 410 (6825), 259.

482

(14) Bateman, A. P.; Bertram, A. K.; Martin, S. T., Hygroscopic Influence on the

483

Semisolid-to-Liquid Transition of Secondary Organic Materials. J Phys Chem A 2015, 119 (19),

484

4386-95.

485

(15) Zobrist, B.; Marcolli, C.; Pedernera, D. A.; Koop, T., Do atmospheric aerosols form

486

glasses? Atmospheric Chemistry and Physics 2008, 8 (17), 5221-5244.

487

(16) Shalaev, E. Y.; Franks, F.; Echlin, P., Crystalline and Amorphous Phases in the Ternary

488

System Water−Sucrose−Sodium Chloride. Journal of Physical Chemistry 1996, 100 (100),

489

1144-1152.

490

(17) He, X.; Fowler, A.; Toner, M., Water activity and mobility in solutions of glycerol and small

491

molecular weight sugars: Implication for cryo- and lyopreservation. Journal of Applied Physics

492

2006, 100 (7), 074702.

493

(18) Mikhailov, E.; Vlasenko, S.; Martin, S. T.; Koop, T.; Poschl, U., Amorphous and crystalline

494

aerosol particles interacting with water vapor: conceptual framework and experimental

495

evidence for restructuring, phase transitions and kinetic limitations. Atmospheric Chemistry

496

and Physics 2009, 9 (24), 9491-9522.

497

(19) Marshall, F. H.; Miles, R. E. H.; Song, Y. C.; Ohm, P. B.; Power, R. M.; Reid, J. P.;

498

Dutcher, C. S., Diffusion and reactivity in ultraviscous aerosol and the correlation with particle

499

viscosity. Chem Sci 2016, 7 (2), 1298-1308.

500

(20) Zobrist, B.; Soonsin, V.; Luo, B. P.; Krieger, U. K.; Marcolli, C.; Peter, T.; Koop, T.,

501

Ultra-slow water diffusion in aqueous sucrose glasses. Physical chemistry chemical physics :

502

PCCP 2011, 13 (8), 3514-26. 23



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 35

503

(21) Tong, H. J.; Reid, J. P.; Bones, D. L.; Luo, B. P.; Krieger, U. K., Measurements of the

504

timescales for the mass transfer of water in glassy aerosol at low relative humidity and ambient

505

temperature. Atmospheric Chemistry and Physics 2011, 11 (10), 4739-4754.

506

(22) Bones, D. L.; Reid, J. P.; Lienhard, D. M.; Krieger, U. K., Comparing the mechanism of

507

water condensation and evaporation in glassy aerosol. Proceedings of the National Academy

508

of Sciences of the United States of America 2012, 109 (29), 11613-8.

509

(23) Tang, M. J.; Shiraiwa, M.; Poschl, U.; Cox, R. A.; Kalberer, M., Compilation and

510

evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere:

511

Volume 2. Diffusivities of organic compounds, pressure-normalised mean free paths, and

512

average Knudsen numbers for gas uptake calculations. Atmospheric Chemistry & Physics

513

Discussions 2015, 15 (4), 5461-5492.

514

(24) Gibson, E. R.; Hudson, P. K.; Grassian, V. H., Physicochemical properties of nitrate

515

aerosols: implications for the atmosphere. J Phys Chem A 2006, 110 (42), 11785-99.

516

(25) Tang,

517

REFRACTIVE-INDEXES OF AQUEOUS SULFATES AND SODIUM-NITRATE DROPLETS

518

OF ATMOSPHERIC IMPORTANCE. Journal of Geophysical Research-Atmospheres 1994, 99

519

(D9), 18801-18808.

520

(26) Hoffman, R. C.; Laskin, A.; Finlayson-Pitts, B. J., Sodium nitrate particles: physical and

521

chemical properties during hydration and dehydration, and implications for aged sea salt

522

aerosols. Journal of Aerosol Science 2004, 35 (7), 869-887.

523

(27) Gysel, M.; Weingartner, E.; Baltensperger, U., Hygroscopicity of aerosol particles at low

524

temperatures. 2. Theoretical and experimental hygroscopic properties of laboratory generated

I.

N.;

Munkelwitz,

H.

R.,

WATER

ACTIVITIES,

DENSITIES,

AND

24


Page 25 of 35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


525

aerosols. 2002, 36 (1), 63-68.

526

(28) Lee, C. T.; Hsu, W. C., THE MEASUREMENT OF LIQUID WATER MASS ASSOCIATED

527

WITH COLLECTED HYGROSCOPIC PARTICLES. Journal of Aerosol Science 2000, 31 (2),

528

189-197.

529

(29) Mcinnes, L. M.; Quinn, P. K.; Covert, D. S.; Anderson, T. L., Gravimetric analysis, ionic

530

composition, and associated water mass of the marine aerosol. Atmospheric Environment

531

1996, 30 (6), 869-884.

532

(30) Li, Y. J.; Liu, P. F.; Bergoend, C.; Bateman, A. P.; Martin, S. T., Rebounding Hygroscopic

533

Inorganic Aerosol Particles: Liquids, Gels, and Hydrates. Aerosol Science & Technology 2017,

534

(3).

535

(31) Tang, I. N.; Fung, K. H., Hydration and Raman scattering studies of levitated

536

microparticles: Ba(NO3)2, Sr(NO3)2, and Ca(NO3)2. Journal of Chemical Physics 1997, 106

537

(5), 1653-1660.

538

(32) Liu, Y.; Zhiwei Yang, ‖; Yury Desyaterik; †, P. L. G.; Wang, H.; Alexander Laskin,

539

Hygroscopic Behavior of Substrate-Deposited Particles Studied by micro-FT-IR Spectroscopy

540

and Complementary Methods of Particle Analysis. Analytical Chemistry 2008, 80 (3), 633.

541

(33) And, S. L. C.; Brimblecombe, P.; Wexler, A. S., Thermodynamic Model of the System H+

542

− NH4+− Na+ −SO42-−NO3- − Cl-− H2O at 298.15 K. J Phys Chem A 1998, 102 (12),

543

2155-2171.

544

(34) Lei, T.; Zuend, A.; Wang, W. G.; Zhang, Y. H.; Ge, M. F., Hygroscopicity of organic

545

compounds from biomass burning and their influence on the water uptake of mixed

546

organic-ammonium sulfate aerosols. Atmospheric Chemistry & Physics 2014, 14 (8), 25



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 35

547

11625-11663.

548

(35) Robinson, C. B.; Schill, G. P.; Tolbert, M. A., Optical growth of highly viscous

549

organic/sulfate particles. Journal of Atmospheric Chemistry 2014, 71 (2), 145-156.

550

(36) Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H., Influence of particle-phase

551

state on the hygroscopic behavior of mixed organic–inorganic aerosols. Atmospheric

552

Chemistry and Physics 2015, 15 (9), 5027-5045.

553

(37) Zhang, R.; Khalizov, A.; Wang, L.; Hu, M.; Xu, W., Nucleation and growth of nanoparticles

554

in the atmosphere. Chemical reviews 2012, 112 (3), 1957-2011.

555

(38) Murray, B. J., Inhibition of ice crystallisation in highly viscous aqueous organic acid

556

droplets. Atmospheric Chemistry & Physics 2008, 8 (17), 5423-5433.

557

(39) Zhao, H.; Jiang, X.; Lin, D., Contribution of methane sulfonic acid to new particle

558

formation in the atmosphere. Chemosphere 2017, 174, 689-699.

559

(40) Shao, X.; Zhang, Y.; Pang, S. F.; Zhang, Y. H., Vacuum FTIR Observation on

560

Hygroscopic Properties and Phase Transition of Malonic Acid Aerosols. Chemical Physics

561

2016. 2016

562

(41) Leng, C. B.; Pang, S. F.; Zhang, Y.; Cai, C.; Liu, Y.; Zhang, Y. H., Vacuum FTIR

563

Observation on the Dynamic Hygroscopicity of Aerosols under Pulsed Relative Humidity.

564

Environmental science & technology 2015, 49 (15), 9107-15.

565

(42) Ottenhof, M. A.; MacNaughtan, W.; Farhat, I. A., FTIR study of state and phase

566

transitions of low moisture sucrose and lactose. Carbohydrate Research 2003, 338 (21),

567

2195-2202.

568

(43) Han, J. H.; Martin, S. T., Heterogeneous nucleation of the efflorescence of (NH4)(2)SO4 26


Page 27 of 35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


569

particles

570

Research-Atmospheres 1999, 104 (D3), 3543-3553.

571

(44) Pant, A.; Parsons, M. T.; Bertram, A. K., Crystallization of aqueous ammonium sulfate

572

particles internally mixed with soot and kaolinite: Crystallization relative humidities and

573

nucleation rates. The Journal of Physical Chemistry A 2006, 110 (28), 8701-8709.

574

(45) Ren, H. M.; Cai, C.; Leng, C. B.; Pang, S. F.; Zhang, Y. H., Nucleation Kinetics in Mixed

575

NaNO3/Glycerol Droplets Investigated with the FTIR-ATR Technique. The journal of physical

576

chemistry. B 2016, 120 (11), 2913-20.

577

(46) Dette, H. P.; Koop, T., Glass Formation Processes in Mixed Inorganic/Organic Aerosol

578

Particles. J Phys Chem A 2015, 119 (19), 4552.

579

(47) Altaf, M. B.; Freedman, M. A., Effect of Drying Rate on Aerosol Particle Morphology.

580

Journal of Physical Chemistry Letters 2017, 8 (15).

581

(48) Pant, A.; Parsons, M. T.; Bertram, A. K., Crystallization of aqueous ammonium sulfate

582

particles internally mixed with soot and kaolinite: crystallization relative humidities and

583

nucleation rates. J Phys Chem A 2006, 110 (28), 8701-9.

584

(49) Williams,

585

BEHAVIOUR ARISING FROM A SIMPLE EMPIRICAL DECAY FUNCTION. Transactions of

586

the Faraday Society 1970, 66 (565P), 80-&.

587

(50) Rickards, A. M.; Song, Y. C.; Miles, R. E.; Preston, T. C.; Reid, J. P., Variabilities and

588

uncertainties in characterising water transport kinetics in glassy and ultraviscous aerosol.

589

Physical chemistry chemical physics : PCCP 2015, 17 (15), 10059-73.

590

(51) Koop, T.; Bookhold, J.; Shiraiwa, M.; Pöschl, U., Glass transition and phase state of

internally

mixed with

G.; Watts, D.

Al2O3,

C.,

TiO2,

and

ZrO2.

Journal of Geophysical

NON-SYMMETRICAL DIELECTRIC RELAXATION

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organic compounds: dependency on molecular properties and implications for secondary

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organic aerosols in the atmosphere. Physical Chemistry Chemical Physics 2011, 13 (43),

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19238-19255.

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613

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Figure 1. FTIR spectra of pure NaNO3 droplets (a) and mixed sucrose/NaNO3

616

droplets with OIR of 1:4 (b) and 1:1 (c) during the dehumidifying process.

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Page 30 of 35

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Figure 2. The measured mass growth factors and E-AIM model calculations as a

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function of RH for pure NaNO3 and pure sucrose particles (panel a and b), and

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mixtures of sucrose and NaNO3 with OIR of 1:4 (panel c) and 1:1 (panel d). In this

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study, the green curve shows E-AIM predictions during a hydration experiment.

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Figure 3. Efflorescence ratio for pure NaNO3 droplets (black) and mixed

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sucrose/NaNO3 droplets (red, OIR=1:4; blue, OIR=1:8) as a function of RH in the

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linear RH decreasing process. The filled area refers to efflorescence RH range. The

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particle size distribution is ~2-8 µm at room condition (50% RH) and the mean radius

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is 3 µm.

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Page 32 of 35

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Figure 4. Measured liquid water content for 1:1 sucrose/NaNO3 droplets as a function

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of RH during downward RH pulse (colorful). The top inset (colorful) shows eight

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downward RH pulses with time. The particle size distribution is ~2-8 µm at room

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condition (50% RH) and the mean radius is 3 µm.

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Figure 5. The RH dependence of the ratio of the half-times for the liquid water

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content to the RH changes for 1:1 sucrose/NaNO3 droplets. The filled triangles denote

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the initial RH and the open triangles denote the final RH with different colors

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corresponding to humidification (orange) and dehumidification (blue) process. The

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area of oblique line refers to the RH region of water transport limitation, and the

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shaded area is relevant to the degree of the limitation. The particle size distribution is

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~2-8 µm at room condition (50% RH) and the mean radius is 3 µm.

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Figure 6. Fitted values for the characteristic relaxation timescale, τ, for various RH

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step changes for 1:1 sucrose/NaNO3 droplets (blue circles), 1:2 sucrose/NaNO3

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droplets (black circles) and aqueous sucrose droplets (red triangles). The direction of

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the arrow represents the RH change with the points indicating the initial and final RH

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between which the RH is changing. The particle size distribution is ~2-8 µm at room

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condition (50% RH) and the mean radius is 3 µm.

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Table of Contents Image

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