Chemi-ionization: Difference between revisions

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The majority of chemi-ionization occurs in the base of the flame.

Chemi-ionization is the formation of an ion through the reaction of a gas phase atom or molecule with an atom or molecule in an excited state while also creating new bonds.^[1]^[2] This process is helpful in mass spectrometry because it creates unique bands that can be used to identify molecules. ^[3] This process is extremely common in nature as it is considered the primary inital reaction in flames.

Reactions

Chemi-ionization can be represented by

G^{*}+M\to M^{+\bullet }+e^{-}+G

where G is the excited state species (indicated by the superscripted asterisk), and M is the species that is ionized by the loss of an electron to form the radical cation (indicated by the superscripted "plus-dot").

The most common example of A-type chemi-ionization occurs in hydrocarbon flame. The reaction can be represented as

$O+CH\longrightarrow HCO^{+}+e^{-}$ ^[4]

This reaction is is present in any hydrocarbon flame and can account for deviation in the amount of expected ions from thermodynamic equilibrium. ^[5] This can then lead to B-type chemi-ionization which can be represented as

$HCO^{+}+e^{-}\longrightarrow {\binom {H_{3}O^{+}}{C_{3}H_{3}}}+M\longrightarrow M^{+}+products$

As well as

$CH+O+M\longrightarrow CHO+M^{*}\longrightarrow M+hv$

Where M* represents a radical metal ion.

References

^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "chemi-ionization". doi:10.1351/goldbook.C01044 C01044
^ Klucharev, A. N. (1993), "Chemi-ionization processes", Physics-Uspekhi, 36 (6): 486, Bibcode:1993PhyU...36..486K, doi:10.1070/PU1993v036n06ABEH002162
^ Dyke, John M.; Shaw, Andrew M.; Wright, Timothy G. (1994). "Study of Chemiionization Reactions in the O + 2-Butyne Reaction Mixture". The Journal of Physical Chemistry. 98 (25): 6327–6331. doi:10.1021/j100076a016. ISSN 0022-3654.
^ Vinckier, C.; Gardner, Michael P.; Bayes, Kyle D. (1977). "A study of chemi-ionization in the reaction of oxygen atoms with acetylene". The Journal of Physical Chemistry. 81 (23): 2137–2143. doi:10.1021/j100538a001. ISSN 0022-3654.
^ Fontijn, A.; Miller, W.J.; Hogan, J.M. (1965). "Chemi-ionization and chemiluminescence in the reaction of atomic oxygen with C2H2, C2D2, and C2H4". Symposium (International) on Combustion. 10 (1): 545–560. doi:10.1016/S0082-0784(65)80201-6. ISSN 0082-0784.

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[1] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "chemi-ionization". doi:10.1351/goldbook.C01044 C01044

[Klucharev1993-2] Klucharev, A. N. (1993), "Chemi-ionization processes", Physics-Uspekhi, 36 (6): 486, Bibcode:1993PhyU...36..486K, doi:10.1070/PU1993v036n06ABEH002162

[DykeShaw1994-3] Dyke, John M.; Shaw, Andrew M.; Wright, Timothy G. (1994). "Study of Chemiionization Reactions in the O + 2-Butyne Reaction Mixture". The Journal of Physical Chemistry. 98 (25): 6327–6331. doi:10.1021/j100076a016. ISSN 0022-3654.

[VinckierGardner1977-4] Vinckier, C.; Gardner, Michael P.; Bayes, Kyle D. (1977). "A study of chemi-ionization in the reaction of oxygen atoms with acetylene". The Journal of Physical Chemistry. 81 (23): 2137–2143. doi:10.1021/j100538a001. ISSN 0022-3654.

[FontijnMiller1965-5] Fontijn, A.; Miller, W.J.; Hogan, J.M. (1965). "Chemi-ionization and chemiluminescence in the reaction of atomic oxygen with C2H2, C2D2, and C2H4". Symposium (International) on Combustion. 10 (1): 545–560. doi:10.1016/S0082-0784(65)80201-6. ISSN 0082-0784.

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@@ Line 1: / Line 1: @@
 {{Distinguish|chemical ionization}}
 [[File:Chemi-ionization.jpg|thumb|The majority of chemi-ionization occurs in the base of the flame.]]
-'''Chemi-ionization''' is the formation of an [[ion]] through the reaction of a gas phase [[atom]] or [[molecule]] with an atom or molecule in an [[excited state]] while also creating new bonds.<ref>{{GoldBookRef|title=chemi-ionization|file= C01044}} C01044</ref><ref name=Klucharev1993>{{citation | last = Klucharev | first =  A. N. | year = 1993 | title = Chemi-ionization processes | journal = Physics-Uspekhi | volume = 36 | pages = 486 | doi = 10.1070/PU1993v036n06ABEH002162 |bibcode = 1993PhyU...36..486K | issue = 6 }}</ref> This process is helpful in [[mass spectrometry]] because it creates unique bands that can be used to identify molecules. <ref name="DykeShaw1994">{{cite journal|last1=Dyke|first1=John M.|last2=Shaw|first2=Andrew M.|last3=Wright|first3=Timothy G.|title=Study of Chemiionization Reactions in the O + 2-Butyne Reaction Mixture|journal=The Journal of Physical Chemistry|volume=98|issue=25|year=1994|pages=6327–6331|issn=0022-3654|doi=10.1021/j100076a016}}</ref>
+'''Chemi-ionization''' is the formation of an [[ion]] through the reaction of a gas phase [[atom]] or [[molecule]] with an atom or molecule in an [[excited state]] while also creating new bonds.<ref>{{GoldBookRef|title=chemi-ionization|file= C01044}} C01044</ref><ref name=Klucharev1993>{{citation | last = Klucharev | first =  A. N. | year = 1993 | title = Chemi-ionization processes | journal = Physics-Uspekhi | volume = 36 | pages = 486 | doi = 10.1070/PU1993v036n06ABEH002162 |bibcode = 1993PhyU...36..486K | issue = 6 }}</ref> This process is helpful in [[mass spectrometry]] because it creates unique bands that can be used to identify molecules. <ref name="DykeShaw1994">{{cite journal|last1=Dyke|first1=John M.|last2=Shaw|first2=Andrew M.|last3=Wright|first3=Timothy G.|title=Study of Chemiionization Reactions in the O + 2-Butyne Reaction Mixture|journal=The Journal of Physical Chemistry|volume=98|issue=25|year=1994|pages=6327–6331|issn=0022-3654|doi=10.1021/j100076a016}}</ref> This process is extremely common in nature as it is considered the primary inital reaction in flames.
 ==Reactions==
@@ Line 8: / Line 8: @@
 where G is the excited state species (indicated by the superscripted asterisk), and M is the species that is ionized by the loss of an [[electron]] to form the [[Radical (chemistry)|radical]] [[cation]] (indicated by the superscripted "plus-dot").
-The most common example of chemi-ionization occurs in hydrocarbon flame. The reaction can be represented as
+The most common example of A-type chemi-ionization occurs in hydrocarbon flame. The reaction can be represented as
 <math>O + CH \longrightarrow HCO^+ + e^-</math> <ref name="VinckierGardner1977">{{cite journal|last1=Vinckier|first1=C.|last2=Gardner|first2=Michael P.|last3=Bayes|first3=Kyle D.|title=A study of chemi-ionization in the reaction of oxygen atoms with acetylene|journal=The Journal of Physical Chemistry|volume=81|issue=23|year=1977|pages=2137–2143|issn=0022-3654|doi=10.1021/j100538a001}}</ref>
-This reaction is is present in any hydrocarbon flame and can account for deviation in the amount of expected ions from thermodynamic equilibrium. <ref name="FontijnMiller1965">{{cite journal|last1=Fontijn|first1=A.|last2=Miller|first2=W.J.|last3=Hogan|first3=J.M.|title=Chemi-ionization and chemiluminescence in the reaction of atomic oxygen with C2H2, C2D2, and C2H4|journal=Symposium (International) on Combustion|volume=10|issue=1|year=1965|pages=545–560|issn=00820784|doi=10.1016/S0082-0784(65)80201-6}}</ref>
+This reaction is is present in any hydrocarbon flame and can account for deviation in the amount of expected ions from thermodynamic equilibrium. <ref name="FontijnMiller1965">{{cite journal|last1=Fontijn|first1=A.|last2=Miller|first2=W.J.|last3=Hogan|first3=J.M.|title=Chemi-ionization and chemiluminescence in the reaction of atomic oxygen with C2H2, C2D2, and C2H4|journal=Symposium (International) on Combustion|volume=10|issue=1|year=1965|pages=545–560|issn=00820784|doi=10.1016/S0082-0784(65)80201-6}}</ref> This can then lead to B-type chemi-ionization which can be represented as
+<math>HCO^+ + e^- \longrightarrow \binom{H_3O^+}{C_3H_3} + M \longrightarrow M^+ + products </math>
+As well as
+<math>CH+O+M\longrightarrow CHO + M^* \longrightarrow M + hv</math>
+Where M* represents a radical metal ion.
 ==See also==