DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules

Abstract

Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of subcritical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here we extend the kinetic derivation of the first nucleation theorem to give a general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.

Authors:
 [1];  [2];  [1];  [1]
  1. Univ. of Eastern Finland, Kuopio (Finland). Dept. of Applied Physics
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Biological, Environmental & Climate Sciences Dept.
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1169565
Alternate Identifier(s):
OSTI ID: 1228465
Report Number(s):
BNL-107379-2015-JA
Journal ID: ISSN 0021-9606; JCPSA6; R&D Project: 2016-BNL-EE630EECA-Budg; KP1701000; TRN: US1500476
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; nucleation; kinetic nucleation theorems; law of mass action; atmospheric new particle formation

Citation Formats

Malila, Jussi, McGraw, Robert, Laaksonen, Ari, and Lehtinen, Kari E. J. Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules. United States: N. p., 2015. Web. doi:10.1063/1.4905213.
Malila, Jussi, McGraw, Robert, Laaksonen, Ari, & Lehtinen, Kari E. J. Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules. United States. https://doi.org/10.1063/1.4905213
Malila, Jussi, McGraw, Robert, Laaksonen, Ari, and Lehtinen, Kari E. J. Wed . "Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules". United States. https://doi.org/10.1063/1.4905213. https://www.osti.gov/servlets/purl/1169565.
@article{osti_1169565,
title = {Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules},
author = {Malila, Jussi and McGraw, Robert and Laaksonen, Ari and Lehtinen, Kari E. J.},
abstractNote = {Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of subcritical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here we extend the kinetic derivation of the first nucleation theorem to give a general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.},
doi = {10.1063/1.4905213},
journal = {Journal of Chemical Physics},
number = 1,
volume = 142,
place = {United States},
year = {Wed Jan 07 00:00:00 EST 2015},
month = {Wed Jan 07 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Critical cluster size cannot in practice be determined by slope analysis in atmospherically relevant applications
journal, November 2014


Nucleation in the presence of air ions and aerosol particles
book, January 1996


Homogeneous nucleation in spatially inhomogeneous systems
journal, November 1990

  • Shi, G.; Seinfeld, J. H.; Okuyama, K.
  • Journal of Applied Physics, Vol. 68, Issue 9
  • DOI: 10.1063/1.346160

Influence of aerosol lifetime on the interpretation of nucleation experiments with respect to the first nucleation theorem
journal, January 2013


A Condensation Feedback Mechanism for Oscillatory Nucleation and Growth
journal, January 1984


Kinetic extensions of the nucleation theorem
journal, May 2003

  • McGraw, Robert; Wu, David T.
  • The Journal of Chemical Physics, Vol. 118, Issue 20
  • DOI: 10.1063/1.1565098

Aerosol-assisted synthesis and assembly of nanoscale building blocks
journal, January 2013

  • Motl, Nathan E.; Mann, Amanda K. P.; Skrabalak, Sara E.
  • Journal of Materials Chemistry A, Vol. 1, Issue 17
  • DOI: 10.1039/c3ta01703f

On the roles of sulphuric acid and low-volatility organic vapours in the initial steps of atmospheric new particle formation
journal, January 2010


The Role of Sulfuric Acid in Atmospheric Nucleation
journal, March 2010


Transient kinetics of nucleation
journal, February 1990


Forms and applications of the nucleation theorem
journal, July 2006

  • Kashchiev, Dimo
  • The Journal of Chemical Physics, Vol. 125, Issue 1
  • DOI: 10.1063/1.2210483

The multistate kinetics of nucleation in the presence of an aerosol a)b)
journal, March 1983

  • McGraw, Robert; Marlow, William H.
  • The Journal of Chemical Physics, Vol. 78, Issue 5
  • DOI: 10.1063/1.445007

Rethinking the application of the first nucleation theorem to particle formation
journal, March 2012

  • Vehkamäki, Hanna; McGrath, Matthew J.; Kurtén, Theo
  • The Journal of Chemical Physics, Vol. 136, Issue 9
  • DOI: 10.1063/1.3689227

A molecular based derivation of the nucleation theorem
journal, September 2000

  • Bowles, R. K.; McGraw, R.; Schaaf, P.
  • The Journal of Chemical Physics, Vol. 113, Issue 11
  • DOI: 10.1063/1.1288802

Dependence of nucleation rates on sulfuric acid vapor concentration in diverse atmospheric locations
journal, January 2008

  • Kuang, C.; McMurry, P. H.; McCormick, A. V.
  • Journal of Geophysical Research, Vol. 113, Issue D10
  • DOI: 10.1029/2007JD009253

Sulfuric acid nucleation: power dependencies, variation with relative humidity, and effect of bases
journal, January 2012

  • Zollner, J. H.; Glasoe, W. A.; Panta, B.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 10
  • DOI: 10.5194/acp-12-4399-2012

Cluster activation theory as an explanation of the linear dependence between formation rate of 3nm particles and sulphuric acid concentration
journal, January 2006

  • Kulmala, M.; Lehtinen, K. E. J.; Laaksonen, A.
  • Atmospheric Chemistry and Physics, Vol. 6, Issue 3
  • DOI: 10.5194/acp-6-787-2006

Nucleation in a nonuniform vapor
journal, September 1976

  • Becker, Carol; Reiss, H.
  • The Journal of Chemical Physics, Vol. 65, Issue 6
  • DOI: 10.1063/1.433390

Binary nucleation of sulfuric acid-water: Monte Carlo simulation
journal, April 1998

  • Kusaka, I.; Wang, Z. -G.; Seinfeld, J. H.
  • The Journal of Chemical Physics, Vol. 108, Issue 16
  • DOI: 10.1063/1.476097

Homogeneous nucleation in inhomogeneous media. I. Nucleation in a temperature gradient
journal, November 2003

  • Reguera, David; Rubı́, J. M.
  • The Journal of Chemical Physics, Vol. 119, Issue 18
  • DOI: 10.1063/1.1614776

New particle formation in the presence of an aerosol
journal, January 1979


Thermodynamics and kinetics of atmospheric aerosol particle formation and growth
journal, January 2012

  • Vehkamäki, Hanna; Riipinen, Ilona
  • Chemical Society Reviews, Vol. 41, Issue 15
  • DOI: 10.1039/c2cs00002d

Kinetische Behandlung der Keimbildung in übersättigten Dämpfen
journal, January 1935


Oxidation Products of Biogenic Emissions Contribute to Nucleation of Atmospheric Particles
journal, May 2014


On the Interpretation of Quantitative Experimental Data on Nucleation Rates Using Classical Nucleation Theory
journal, November 2006

  • Sear, Richard P.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 43
  • DOI: 10.1021/jp064692a

Molecular understanding of sulphuric acid–amine particle nucleation in the atmosphere
journal, October 2013

  • Almeida, João; Schobesberger, Siegfried; Kürten, Andreas
  • Nature, Vol. 502, Issue 7471
  • DOI: 10.1038/nature12663

Cloud condensation nuclei production associated with atmospheric nucleation: a synthesis based on existing literature and new results
journal, January 2012

  • Kerminen, V. -M.; Paramonov, M.; Anttila, T.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 24
  • DOI: 10.5194/acp-12-12037-2012

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation
journal, August 2011

  • Kirkby, Jasper; Curtius, Joachim; Almeida, João
  • Nature, Vol. 476, Issue 7361
  • DOI: 10.1038/nature10343

Nucleation of a new phase for particles with finite lifetimes
journal, October 1990


Some consequences of the nucleation theorem for binary fluids
journal, May 1995

  • Oxtoby, David W.; Laaksonen, Ari
  • The Journal of Chemical Physics, Vol. 102, Issue 17
  • DOI: 10.1063/1.469121

Measurement of the molecular content of binary nuclei. III. Use of the nucleation rate surfaces for the water‐ n ‐alcohol series
journal, September 1995

  • Strey, R.; Viisanen, Y.; Wagner, P. E.
  • The Journal of Chemical Physics, Vol. 103, Issue 10
  • DOI: 10.1063/1.470672

Formation of nanoparticles of blue haze enhanced by anthropogenic pollution
journal, October 2009

  • Zhang, R.; Wang, L.; Khalizov, A. F.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 42
  • DOI: 10.1073/pnas.0910125106

Growth of atmospheric nano-particles by heterogeneous nucleation of organic vapor
journal, January 2013


The Problem of Measuring Homogeneous Nucleation Rates and the Molecular Contents of Nuclei: Progress in the Form of Nucleation Pulse Measurements
journal, August 1994

  • Strey, R.; Wagner, P. E.; Viisanen, Y.
  • The Journal of Physical Chemistry, Vol. 98, Issue 32
  • DOI: 10.1021/j100083a003