J. Mass Spectrom. Soc. Jpn.

Vol. 58, No. 3, 2010

REVIEW 
 7   !"Fundamentals of Mass Spectrometry
ῌGas Phase Ion/Molecule Reactionsῌ
Kenzo H>G6D@6  Clean Energy Research Center, University of Yamanashi,

Kofu, YAMANASHI, JAPANThe ionization is the ﬁrst step for the mass spectrometry. The ion/molecule reactions play major roles not
only in the gas-phase chemical ionization but also in the ionization processes in condensed phases, e.g., secondary
ion mass spectrometry (SIMS), matrix-assisted laser desorption/ionization (MALDI), electrospray ionization(ESI), ﬁeld desorption (FD), and ﬁeld ionization (FI). In general, the mass spectra obtained by various ionization
methods reﬂect the outcome of complex ion/molecule reactions taking place in the respective ionization method.
Thus, fundamental knowledge on the ion/molecule reactions is indispensable to make the mass spectrometry as
the superb analytical technique. In this chapter, the fundamentals of ion/molecule reactions will be described.
(Received January 27, 2010; Accepted January 28, 2010)x

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1.45
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3.78

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ionization

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Horning I3t4uvQ (APCI) 23), 24)

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H2OSSH2OWH3OSSOH
S

CH4SH

HS(H2O)nV1SH2OSN2WHS(H2O)nSN2
N4 SC6H6WC6H6 S2N2SS

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CH3SSH2ῌ H῍῍ C S ῌH(12) zY:{|Z S

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H

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 (18)

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! 3h"'QL9:=>?@ABC (RE) 33

Q?4Q

 3 tight complex +Rj#_ A

E$1L" 5IJ::z³L- ´¹S2 3TtI"O32), 35), 36)@ABC (IE)

' #B Q' ::zB'62 ¬­|­! " 22 x7$wx " U"c)J89@ABC +Q)JC : ;@ABC- 3n%X

@AB

' 4 IJL3c#4Xµ2¶ H ,!
<'¬­

 (18) '2'tight complex ´3 <'@~º»¨V+@~º¼W sLK?L3Rj#´¹

M'@~º3»¨- #4

῎ 96 ῎Rj#tight complex ´'½'O.³3

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 

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

1,000 '12

cm molecule

1* %+

s'1

 300 K %$ 1.4&

10'11 cm3 molecule'1 s'1 ()



100 

12345  45 $  67%;  % <=>? @

>?.%

 89:

%NO 

t-C4H9PP(C2H5)3NQ(C2H5)3NHPPi-C4H8,[M] 45

 kt $ %#6M*37) !"# ¦U1 3   H3OP
438)

H3OPPH2OPCH4QH3OP(H2O)PCH4
ktQ3.7&10

'17

4

'2

6

/T cm molecule

s

(25)

'1

(26)

 78$ &%$4§ AP  B

9Nabc

deH4Iabcde ¨k , !
r

(19)

y

 kt $ T 45   (25)

k $ 300 K, 640

K % FG 1.6&10'9 H4I 1.5&10'9 cm3 molecule'1
s'1 % JKL 6M  )$  3 T 6M1 &JL#  (6 A%+ B

 !"#CDE (19)

/0 3 ¤%+1¥3   45 ! 3 ¤

1* , 200 K -.% 1.1&10'9 cm3 molecule'1 s'1

/0)

¤

(24)

[AP], [B] H4I [M] 3: F 1

 $ (20)'1

3

kc ks [M]Qkt [M]
kb

kfQ



  !"#  (17)

 k $ 640 K %$ 1.7&10()

 complex'[ [ABP]῎abcde2¨k

7B

, 7

2.2.4 ῌῐ῎῏ῑῒ῍῔ΐ!© [ABP]῎

RSTUV (20) $ $WX:4 )MkBª; " qr%+ (&J

3  M  ) 1 %+kf

APPBPM Y ABPPM

(20)
(21)

kb

P

ks

P

[AB ]῎PM Y AB PM

B$ AP  B<«* B$  (24) =
, 

]

) )M 

kt

*

#

bcde (V) $­T M
 (V῍T *(V῍T *  3 4 i

 ks $ 3  M(vww (­T*

 M



4 ^`!abcde (\!^_ ][ ab

kb

*

qr%

¯?q:  MV) ±Aabcde (V῍R)

ww{_kB:`%+ f 3 yzvw$ yzw |m1¡[ [AB ]῎ ®a@vww%$

Jqw M ° ®abcde (V῍ qr%+ B$ st uto%3

Hv

¬>6
P

9Nabcde (T) jkBlB# Z[$mnopI AP  B x2yzw  3 L (22)cdefabcde g ῎h*

w



&%¨k

(22)

Z[\:][1^_

&JL:

+

kc

APPB ῌ [ABP]῎¡[4§#/

 k srBrq45 7  kt% ks $(v"$ (24) q"3  C²

D  ) )MX ³$ E´ 39,"!2 }~qr 7 %$yz

40

w$B: !

 45 $·%!eo abcde RSTUV $  3  !6 !"2#µ: )

4§ <·%!`abcdeeo%   $ CDEL

2 w#: %+, !

$%#



* 

3M

 6M1

(&%,% RSTUV (20)1abcdeHlabcde¶;$ Fig. 2

abcde¶; ¸2:& , [ABP]῎!

0  (23) $ (27)c  (21), (22) l" % kc $ APB)w

 (ccollision),P

kb $'[ [AB ]῎ (back dissociation), ks $ [ABP]῎ (b M  ) )M  : q +:$>? k b ¹k s [M]45ºF~
kfQkc

P3, kf $ A  B


_,1

)

(27)

 kc G¡[$ RSTUV (20) $»ql¼ 2 ¤

% [ABP]῎  ;(sstabilization)   % kc H4I ks*$+ kL +:$ kADO %%
 (21), (22) H: [ABP]῎ , 1#  (20)1" (23)

B

-rB

kc ks [M]kfQ
kbPks [M](23)

%  3  M (.#/:e(* Tw  3  M

01 ! *

T &:¡[ [ABP]῎ JKL$ 3  M 4 ;kB AP  B  >? k b ¢k s [M]_,13 % kf $ (24)45£2;kB

Fig. 2.

ῌ 97 ῌHw (E), ® (V), ±A (R), 9N (T) abcdeeo abcdeK. Hiraoka tion) 2 (pseudo 2nd order reac-  kbks [M]  kbks [M] 
!"  N2 # #N2 $N4 #  O2 # #O2$O4# %41) , NH4#, CH3NH3#  (CH3)2NH2# &'()*+(,-./012 3(45
6

 3

2

(789:;<6=

>?@ AB(  '(C53D kf ( E 3 F M (GHI*J (23) KL@M @"42)N44) (9 ,-./012(OPQ RS@"TUVWX< OP(21), (22) YZ[\]^_`9aK"bcd K=
2.2.5 

)*(e+%+f+ gQ h@(ij1K= ij1k3Il`"mY e+%
+f+(n* o= pe+%+(fFig. 3.

O2 (X3 ῌg )  O2  (X2Pg) (1VTUVWX ¡£ TUVWX¤¥ p'µ 45 ¶· ( ¸¹ ῌ1986, Elsevierr

Fig. 4.

L~(+(^)*f+º*»(¼ sa(emax) (cm2)  &   a  f + T U V W X emax(eV) (  ½ p' µ 46   ¶ ·(¸ ¹
ῌ1971 John Wiley & Sonsr+nqK=r e+%+sTUVWXa f+tQ qij1uv w
Q  ij1Ye+%+f+ x`9y(z{(K qij1| }%~Z[Ku
Q%` ("m ij1(`ij1+Y -21X 1LL +(3` ij1YQ ((OPu`
AB#e ῍ AB῎

(28)

AB῎  A#B(29)

AB῎#M  AB#M(30)
AB#e  A##B#e

(31)


AB#X  AB#X#
CI Ko@(32)

(Yf+ (electron

capture) K= L~( `
O2#e  O2

(33)



 O #O(34)

SF6#e  SF6

(35)



(36)

 SF5 #F
CCl4#e  Cl#CCl3(37)

'(f+Y sCf+KYL TUVWX5 p(Fv45r (f+ 
@%` ij1u( ^`
Q  Fig. 3  O2  O2 (1VTU

f+ ¯%tQ

VWX ¡ `45)
u`"mY O2  (v῏$4) (£¢~' O2  O2 (£ ¤¥¦"§Q 
(K f+Y¨ YL O2(v$0) (TUVWXwQ

 ! 0.08 eV sTUVWX O2 





 £

E3

(²Y(9@"ª«(v῏$4) ( O2 uQ%` O2 (v῏$4) Y#¬­®$TUVWXF M °±*Q  v῏$3 `= (v῏$4) (£ ¤¥=(K 0.08 eV (© TUVWXof+ O2 @O2 & Q"  k3 O2

O2#e ῍ O2῎

(38)

O2῎#M  O2#M(39)

f+(³ f+(TUVWX ´ L

῍ 98 ῍u # (eV)

Table 2.

orption/ionization (MALDI), secondary ion mass spect-

23



H
O
F
Cl
Br
I
NO
NO2
NO3
N2O
O2
O3
OH
SCN
SF6
SF5
´}Sµ¶·¸·TW}|¹º´}S»¶ i¶}S»
¼½Wi

0.75
1.46
3.4
3.62
3.37
3.07
0.024
2.43
3.7
0.22
0.5
2.05
1.83
2.17
0.6
2.8
2.83
0.98
0.88
0.66
0.55
0.14

rometry (SIMS), electrospray ionization (ESI) !>  AKr #-E <NO fp #IFHIAK8PstE
 >! # >! >
!WX #u%1 R +,6A>
!-.EQv1 !>HIB71JRwB4f/<NO0fp2eASCT

K (O,  #-./Rx

4 >B  :` 52[55   -./( A ^.y z{|}|<NO~ ]<NO~!>U'6, V!WB
4WO,4'

%,6(A M

Y, v?,%,6Z[B W>55)\]E

1980 X*RE^O, %AJE  _`A ab cd ef Viggiano g ^vhA\]<NO\  # "ij*+$ E :`

1,100 kJ 9,300 -./O,4'%

W>AeDlm!74' _`6 J \]<NO\T ' 

4nsoE p`g A %T'4 q?

 O2   O 

rB4sx4' < ' %, J 

 ! " # (29)$ %!   &#tRwE< -./A u #  &  AB(e ) AOEPst!vwE  %W(B   * (saMAX (cm ))  +,

>'%!B4 %2x fp

 (eMAX (eV)) -.'/0123

U G ¡UB4' < '#'Fig. 4



2

0'45

46)

3.

%16   (cm2)  23
7489' :!%;<!= #O A

# -;yz{ X|} u¢I . u£ 0%!>?1
@; 4 +,6A

. ¤¥¦¥  yz}|B4C DE< A F4§!>{\,gNHK8  V¨ '/0 "GGH !$ I" !1{\,gN

 +,16#JK7 $ %I" !LMB4NO, " Fig. 3  O2

(vP0)  O2(v῍P0) MQ & 0.5 eV$

#-.

0'4|F

3.1 

%,R

 #}©(O,Y>-/u% x

E '/@G STU% 0'4

A ^{ #E % !?ª #W§~

(O,4' '/01@  0'4

2 DH«E %Z0¬!

 Table 25W§~2 DH«47)

2.2.6 

®4#"­ A

}|§~2 DS«¯B  DG«PDH«TDS«, -.16V) *+,! #WX +-.
#48)[50);

%K8¬b^ #!6 °±3

3452\6E78 ]' H, H2, H2 ^ #51)

(RE) 

#2 (IE) J!>  9_A:`a;O, '% X|}^ # AH((BPA(BH( !6 B X

2.2.7 %Y1Z1 2' SN2#d~2 DG«E
!$/ 0'40,<Ab=>3?E 16|} A J
6cd@eAf'4 #$B,!Cgh  3452\ ij2\ kDl\ Emnol\!

<'<'% ¤¥¦¥^

 # A((BHPAH(B( !6 A( ¤¥¦¥ B( J <'% K8¬!

%

! # A((BPC((D, W§~> fpeAIF G A  #I

2 DH«² JA  #%yz{ DHf«16³

FHIJ4f/%KLE  M  <NO

x%E<Q DH«PDHf«(C()(DHf«(D)DHf«(A()

f'4A CI ; APCI AqJ matrix-assisted laser des-DHf«(B) yz{>B

ῌ 99 ῌ

 :`K. Hiraoka

56   

    

DH\-YZO!@0#x|H-"0}s # 7 (42) ^2 DS\-K~%36 !"# $%&'%(

I= Lau f60)#QBJK (NIST Chemistry WebBook, URL: )http://webbook.

bF0n:!@7 _nist.gov/chemistry/*).

^2"8 DS\4L# s 2M O]



3.2





<z}%(#4 1fK~B8 2a(44)4 ;N pO-0;-QB+, -./01 2CI, APCI +.,3!"4 #5,%678 61

=> 3? ion cyclotron resonance,

ICR4 7!@-A"0;%( B

2300 K PQ@t

4 %"0;CD # Torr EF,-GHIJ.,3K%#

DG\ ; a (44) -R

1fYZfOP *#( ms %7!

# $%GHIJEF,# 10

T2

Torr -% &L 8# x$%# keV &LF 2LF'#M#( ms4 )@ +Q # ms R%S,A"%( ICR %s (B1Hh)s (B2)(44)
s (B2Hh)s (B1)b0 _O`DS\rotsymdRln

%9:-/0;% 2<N 7 (42) Sf

B!@0#1fYZB
B^2 DS\

B 7 (42) OJ!n:7%# 7TP%3U(/#2zf! VQ/ OJ!V^2 DS\#pW X/ }  8M12 J/Kmol Y% QB] F (M5 ms)

OP 300M1,000 ms :!

Q/V DG\ῌDH\N ;! 0!z DG\@A"

 # M #.:-78

ῌDH\dPA(B1)TPA(B2).

"

U$0;6V/%#! 7!@"00;OH+0

D W!@0# K -X-YZ;%(YW PA -\]%(% ^_%
ῌPA  H2O OH6X

^2 DH\ _O`^2

DS\;a (40) 23

QB]  a (40) -2eQBa (41) 1f !@0#4#- 1/T

4Q $0 D 2 - van’t Ho# 

$;J4 Wg51f^2 DH\,

1/Td0 %6781f^2 DS\YZf

῎PA  NH3 OH6U( ?  Zb`

 n F 61 1fcdQB@t PA -Table 30 E1f ef grG 



1h-¡¢

!@ i

s F n  2non-bonding 4a44 F

(40)

DH\
DS\
ln KdTh
RTR

? 

῍PA  H2O ; NH3 ;:? p _O``

B van’t Ho# a4 bc 

TRT ln KdDG\dDH\TTDS\# UR1 i Z%(%  -[Q _D !@0# K # 7[1 2 DG\ QB
]



X

(41)

/i

D £EF#i¤¥j-6i% PA k` H2 

B H3h #l¦e¥j-6i pm` CO  C ; O  PA 8# §t

9j!Xkl# 57M59 -m)

594 _O` 426.3 kJ/mol %H ¨0!¥j

B # COHh %#!/ HCOh ;!  # CO o3.3  

.no©p (highest occupied molecular orbital: HOMO)

n:7#7;%6o6<=!
7pi% CI q APCI r!fs MALDI q
SIMS_6>? A"

B]  Rs@t Q-A;

7uBpC;! <=BZ  R%


"0D  !

(B  n:7 (42) !@0# K # a (43) %E
B1HhhB2dB1hB2HhKd[B1][B2Hh]/[B1Hh][B2][1

2 DG\#a (40) %FCf

ªR01f% `m`OH6U(!«-6i 611zfs CO ¬­s®¯°t± C 
(HOMO) ©pr# (CdT Odh), 5s

C ²qu0;³´

0 OJ  # qo.no



©p;

(42)

µ·µ C2H5h # µ¶ p 

ªR0 µ¶ C2H4 (HOMO) ;(43)

 v;w"n:7"0# pix%Q1yz!  7 (42)  B1 ; B2 

% 5s ©p C q r] _H  
;BªRQ vwx¦e¸1¥j

H2CHhCH2 -e0 ¹y¥j H3C῎CH2h #z¨0!

{n|}% B H3Oh #!~  l(proton¦¥j-; NH3 %# ¯º

a$nity: PA) { PA(B1)TPA(B2), #7

 N a4 (HOMO) ;Q

G0 a (40) FC# 7 (42)NH4h °;l»~K¥j-e0 iR^2 DH\[1 2 DG\% van’t Ho# $H l±# NH4h »i H 
῍ 100 ῍wQ/¼½0zp1 
Table 3.
.~
G
He
Ne
Ar
Kr
Xe
O1
H2
O2
N2
CO
CO
CO2
CS2
NO
N2O
N2O
NO2
SO2
O3
H2S
.
.
CH4
C2H6
C2H4
C2H2
C3H8
C3H6
C3H4
C3H4
C4H10
C6H6
C7H8
C10H8
C10H8
C12H10
C14H10C24H12
rC 1
H2O
H2O2
CH2O
CH4O
CH2O2
C2H6O
C2H6O
C2H4O2
C3H8O
C3H8O
C4H4O
C4H8O

 

zp+,-{|}+,-{|}(kJ/mol)

?

He
Ne
Ar
Kr
Xe

177.8
198.8
369.2
424.6
499.6

H2
O2
N2
CO at CCO at O
CO2
CS2NO
N2O at N
N2O at O
NO2
SO2
O3
H2S

422.3
421
493.8
594
426.3
540.5
681.9
531.8
549.8
575.2
591
672.3
625.5
705

CH4
C2H6
CH2CH2C2H2
C3H8CH3CHCH2
H2CCCH2
H3 CCCH
i-C4H10
C6H6
C6H5CH3o-Xylenep-Xylene
Biphenyl
Anthracene
Coronene

543.5
596.3
680.5
641.4
625.7
751.6
775.3
748
677.8
750.4
784
796
794.4
813.6
877.3
861.3

H2O
H2O2
H2CO
CH3OH
HCOOH
C2H5OH
CH3OCH3
CH3COOHn-C3H7OH
i-C3H7OH
Furan
Tetrahydrofuran

691
674.5
712.9
754.3
742
776.4
792
783.7
786.5
793
803.4
822.1

.~

?

C4H10On-C4H9OH
C4H10O
i-C4H9OH
C4H10O(C2H5)2O
C6H6O
C6H5OHC12H24O6
18-Crown-6
r 1
NH3
NH3
CH5N
CH3NH2
C2H7N(CH3)2NH
C3H9N(CH3)3N
C2H3N
CH3CN
C2H7N
C2H5NH2C4H5N
PyrroleC4H9N
Pyrrolidine
C5H5N
Pyridine
C5H11N
Piperidine
C6H7N
C6H5NH2C9H7N
Quinoline
ABC$
C$ k
CH5N3
Guanidine
C2H5NO2
GlycineC3H7NO2
A-Alanine
C3H7NO2S
A-Cysteine
C3H7NO3
A-Serine
C4H4N2O2
UracilC4H5N3O
Cytosine
C4H7NO4
A-Aspartic acid
C4H8N2O3
A-Aspargine
C4H9NO3
A-Threonine
C5H5N5
Adenine
C5H5N5O
Guanine
C5H6N2O2
Thymine
C5H9NO2
A-Proline
C5H9N3
Histamine
C5H10N2O3
A-Glutamine
C5H11NO2
A-Valine
C5H11NO2S
A-Methionine
C6H6N2O
Nicotinamide
C6H9N3O2
A-Histidine
C6H13NO2
A-Leucine
C6H13NO2
A-Isoleucine
C6H14N2O2
A-Lysine
C6H14N4O2
A-Arginine
C9H11NO2
A-Phenylalanine
C9H11NO3
A-Tyrosine
C9H12N2O6
Uridine
C9H13N3O5
Cytidine
C10H13N5O2
Guanosine
C10H13N5O4
Adenosine
C11H12N2O2
A-Tryptophan

 (NH3  CH3NH2  (CH3)2NH  (CH3)3N), PA 
 !"#$ %&'()%*$ ++,-{|}(kJ/mol)
789.2
793.7
828.4
817.3
967
853.6
899
929.5
948.9
779.2
912
875.4
948.3
930
954
882.5
953.2
986.3
886.5
901.6
903.2
914.6
872.7
949.9
908.9
929
922.5
942.8
959.5
880.9
920.5
999.8
937.8
910.6
935.4
918.3
988
914.6
917.4
996
1051
922.9
926
947.6
982.5
993.4
989.3
948.9

:;<= XY!O;THPMNO PA
Z (986.3 kJ/mol)PS [\]-,G+\^O_`ab/"c+dWef]g1 hi+,ij#$ k";lm/"ABCn,-./"01 234567.89. :;

.1<= Table 3 >$ ?@ABC DE$ FG

PA Zopq  PA MNOABCn D?@H$ IJK LMNO PA

ABCnK

PQ$ O:<PE

RPMNO PA (1,051 kJ/mol)PS !"#$ T

.1

HB+,-UV234567.Wῌ 101 ῌhrst_1 MNOij+,-

uv!#wxy<PO

K. Hiraoka

3.4

  AH

&rs!

B tu_Uv* wxy*z{|HU }U~HU+Y*
lDE D= qef&   M62)72) MmL+Y (D῎EA) - Table 4 C



AH

B

A BH

!"

 #$"!%&'"() *!%&

DE A:  P

CI C

=

* AH

+, - .!/0 1* !%*Mjk m+Y- C&-234 [CH3COOH#h&DE+ B H] -56%

7 . * ! % &     - 5 6  8 CH3COOH 956

CH3COO: H  7.

;< 

H2  H

H3 H2 = * >#? H2* H: H:%& CH3COOH ! H2 !  H
H2 CH3COO:

B

O2

e: O: OCH3COOHO2

e: M 3 :

H C- %& CH3COO -56 

I!J" -KLe:(6.5 eV) OH: H

CH4

e:(10 eV) H: CH3

DE
:A2H A1H A2

NH3

e

:

(50)
(51)

jC C2H:, C2:, C:, etc.

*CLM&N-OC 2! CI CPQR

(49)
O2: M 3 

H2ODE  FDEGH 

A1

Z= MmL-C!" *!

!" "@A CH3COOH *!%&:(45) C# DE

H: NH2 or NH2: H

(52)
(53)

C.  S[U\H-MS[U\H(45) C>M&:DE56"ie=!.s

m CI # C$)%K%%&M"M #4&(45)

 STUVH+ DH45W * A῎H XYZS#m DE-56.sC ' !

[U\H D(A῎H) ! Aῌ ]^_U  EA(Aῌ )(   -)#m fc

C#4 ` (46) #$C! B

*+C CI # !%&%%&M "¡"(

DH45W

ῌ

DE£C¤A¥7f.S[+¢M

D(A2῎H):EA(A2 ):D(A1῎H) EA(A1ῌ)

U\H!¦,C#h&'+%lM§(46)

A:  PA(A:)  DH45W!` (47), (48) ¨Cb( baCb  CCl4, NF3, CH3ONO "kb

IE(H) ! ;<cDE+S[

U\H b
DH45W

:

:

CCl4

e: Cl: CCl3(54)

e: F: NF2

(55)

(47)

NF3

PA(A:) D(A῎H):EA(A) IE(H)(48)

CH3ONO e: CH3O: NO` (48)  AHCg %.h&AH,defS[U\H

D(A῎H):EA(A) ieM

jk AH  H -d%lm #$"* AH *nBM!M$!C" o+Y* pDE56©-!%&PA(A2 ):PA(A1 ):DE(45) STUVH+ DHW-q!C#hf( 4lM

(56)
Cl, F, CH3O "kj$oXYZS[U\H#4KnBM(b .!/0 CCl3῎Cl XYS[U\H

CCl4 9 CCl3

Cl,  297 kJ/mol 349 kJ/mol "b Cl c EA(54) 

349:297

52 kJ/mol .' !"
Table 4 /

Table 4.  [D῎EA] [D῎EA] (kJ/mol)

H2
H2O
CH3OH
C2H5OH
DMSO
CH3CN(CH3)2COHF
H2S
C6H5OH
CH3COOHHCOOH
C6H5COOH
HCl
CF3COOH
HBr
HI

361
322
264
256
255
250
236
235
161
151
146
132
112
84
38
42
3

ªK*nBM HI  b DE£ HI«¬ef!

I: DE0:­DE!%&®qef¯2 I DE/
HI °!

%& HI C1±&²'!"( b ³C H:, OH:, CH3O: DE/ST|HU"k*#4nBM(oµH2, H2O, CH3OH -56

-´B2M&

 .' !"DE+e·lMg¶- DE!%&

DEDE

©-DE!%& OH:, CH3O: DE"kM(f =*b H2O, CH3OH "k*M( b ©-DE!%& OH: -&#m56
3#!%& ¸¹º»H H2 bM CH4 /C N2O-4¼%.½C¶#b73) N2O 
!Z

5

-%&7) O: 56%  O:

 H2 bM CH4 (;<c-´B2M& OH: DE
῍ 102 ῍¼½FP()
Table 5.

?@AB'Q:]^_2`a ¸¹º %DHj (kJ/mol) »¹º %DSj (J/mol§K)?@AB


H3 (H2)nN2(N2)nO2(N2)nHe(He)nNO(NO)nH3O(H2O)nCH3OH2(CH3OH)nH(CH3COCH3)(CH3COCH3)nH(C2H5OH)(H2O)nt-C4H9(H2O)nLi(H2O)nNa(H2O)nK(H2O)nRb(H2O)nCs(H2O)nF%(H2O)nCl%(H2O)nBr%(H2O)nI%(H2O)nF%(CO2)n 

n1

n2

n3

n4

n5

n6

n7

n8

n9

28.8
72.7
107.8
87.8
20.9
72.7
227.8
῍
59.4
96.1
146.3
126.2
115.4
122.9
123.7
122.5
100
109
46.8
92
142
96
100
92
71
83
67
88
59
81
97.4
76
61.4
82
48.9
61
43.1
64
135
111.6

13.8
72.7
11.5
62.7
18.8
79.8
15.6
74
53.5
154.7
84.4
98.6
82.8
114.1
51
96.1
80.3
117
῍
῍
109
88
84
92
67
100
59
92
50
92
80.2
93
54.3
89
48.5
75
39.7
74
30.5
76.1

13.2
77.3
11.3
66
17.6
81.9
2.7
53.5
15.9
79.4
74.8
118.7
58.9
104.9
35.5
71.1
59.4
109
74
121
88
105
67
92
54
96
50
100
46
100
64
96
49.3
93
47.7
94
38.5
85
30.1
94.5

7.2
74.8
10.6
69.4
16.7
94.1
2
45.1
23.8
133.8
53.1
97.8
48.5
96.1

6.9
79
10.3
85.7
11.3
67.7

6.4
83.6
9.5
90.7
10.2
67.3

3.7
69
8.5
85.3
9.4
77.3

3.3
74.8
7.8
80.7
8.8
80.6

2.5
79.8
7.4
86.5
7.8
79.8

14.6
104.5
48.5
104.5
41
86.5

17.1
125.4
44.7
109.1
37.2
84.4

12.5
96.1

15.5
112.9

12.1
83.6

῍
῍

54.8
117

46.8
130

46.4
137

  CI  !73)"75)

52.3
109
58
120
67
125
59
105
50
105
46
105
44
105
58.1
111
44.3
95
46
110
38.5
99
24.2
84.9

#$ F &' () (55) *+,  HF
 6

HCl 8-'9:  Cl% ;

51.4
109
39.7
91
45
119

45.6
104
36.8
88
43
118

43.5
109

23.4
93.2

22.2
94.1

16.3
῍

NIST

BxB'H

 (URL: http://webbook.nist.gov/chemistry/).

-./0123!  (Table 4), F% () (45)'45&

50
134
46
109
42
109

~BA 4\   \ ABfm

%

59
130
50
117
46
105
42
105

R1R2HR1HR2

() (57)(57)*' () JPis!() emnkBi; DSj b>s'  ,<=3! > ?@ABC   ¡W cd/ i;o ¢£¤+ ¥!¦!

& DEFG',H ?@AB

4"12 J/mol§K  $¨ () (57)7

'I! JK:
3.5eA

gkBi; DHjcdefghBi; DGj©ª«!


!¬­&\®I¯}! bDGjDHj%TDSj'

4! DSj¤5 ° DGjῌDHjo $±° STU


1.2.3 KL$M;NOFP RH QR:STUT

TVW() C2H5i-C4H10C2H6t-C4H9

Z['*\ () ]^_eAgkBi; DHj {| 56 >s²;_³ yz

2`a bcdefghBi; DGj eAgkBi; DHj&] DHfj p DHj(kJ/mol)[DHfj(C2H6)DHfj

4*lemnkBi; DSjo pqrH (t-C4H9)] % [DHfj (C2H5)  DHfj (t-C4H10)]  [(% 84) VW() XY() (57)s =>s tguvwx yz&] DHfjpqrH {| 56 ' }+  ]^_2(693)]%[(901)(%134)]%158 kJ/mol ´µ

῍ 103 ῍*\ ()¶H·]() b()



eAg

K. Hiraoka DH    79  C2H5  i-C4H10  % t-C4H9

!"#"$



& '

   C2H5 ( )*+,

-





.

S

B

L6M

2

%





%(D 3 / uG+, 7 Nw@% (2) /x A6F-7 2 % (60)  %H ( %T ASn1B

S OPHA6F%HI(EFHI9-7

Q7 [\,* ASn 'G j6 %
0  )*+,1234567
8(-  : 5; )* CH5 <9HI(Nz- R-  %= C2H5 >   -. % (1) <[\,*#o %TST
A Table 5 R- %UV %H*
(DH (kJ/mol)), zUHB2 (DS (J/mol

= (2) )* PA (543.5 J/mol) (123 PAK)) VR-

(625.7 kJ/mol) ?@A7 12B$%C

http://webbook.nist.gov/chemistry/) K 

 C3H9 ( E79pC W     0  (a)H2   E-  HIJ PA

H3, CH5, C2H5   3 X 2 YtS@jZ[CH5C3H8DCH4C3H9 9

F-G i-C3H7



(680.5 kJ/mol) (123 PA (625.7 kJ/mol) ?@'7 C2H5 K C3H8 L12B$T (b) H3 

H2[\,*H3 (H2)n  H3(H2)3(H2)3(H2)2

T  (shell) W

W@j


%(9





K  7    C2H5  ! " # "       (@ji-C3H7 ?@'7 !"#"$

j;j 6  H2

C3H8DC2H6i-C3H7 9+,<N
i-C3H7 % C2H5 0M



%O

 %

    ( P+,4QRS+, AK( +, "<7+,#76$7  V%W&@'X' 

3.6  (c) N2   N2

.[\,* N4

W@j

7( O2  O2
 P(O2)3(O2)n < [\,*{ (e) O2 = (O2)2 (O2)n W@jN2

[\,*( O2  (N2)4 (N2)n j lobe[\,* ( .  ]/  790bS [\,*W (N2)2  (N2)n.79  N2  O2  p῏gW@jj_

`c AKX H3 %`c-zKaj H2

   %E"<N T(Y()* +,-UZ

.\{ H3 j]^( D2h cd@efW (d) O2

  %( TK U!G (URL:

1rW#-

 (f) +, Rg [\,*( (Rg3)(Rg)n W{-^?05M0_01`a bc2- 34 d.ef%O j Rg \Y¡Z¢£

67 e5- [\,* - ` Rg3 {A6  (g) [\,*( 0 67]7E7 

NO(NO)n ( ¤= n ¥= n ?@uG@vGf8g797@h1:? ? tSH¤¥@

¦.NO -cY0i [\,*( h@j ¤= n @j NO (NO)n hYc

1 _01jkl;)*<mG6  [{A6uG-  (h) 12B79 %<70@

\,*79 =>F7G  7]

 12B@79 .H2O F (79 

79A60n?A6 

6itS@ H j-@7( K; f6Ke5- [. b\,*#o %(AnGBpC



H (S)n tSH[\,* n c§MG?¨- Z12B@79 .©B ©BªB# «)7(῎ bq1rW#9s-  0MI,¬­®"  (

 

@07 nD2 uG"¯IW S°H°tS- [\,*#o %( +;D 3 /EF uG+, (22) /

F9

12B@ H . % (20), (21),S {A6 .0 12Baj©BªB#0i [\,*#o %(D 3 /E

±560W H3C῎C²N°H°N²C῎CH3 nῌ

?F-7vwx

A6F-G

mTorr yz([\,*{ +,w

3 y³tSH´¨- (i) F (CO2)n %HIA( nD1 µ7¶j@tS{A6 .·¯¸¹-|[\,*x (J7 CI (= TorrC FCOO nῌ2 (tSklm7nYtS

7K}v7w:?~ +;[\,*#
o % (58) e5Gd0$7

ASMDASM-

A6   oº»7[\,*#o(58) Cl (CO2)n ( nD1 Km7nYtS{

(59)

-

ASnBDASn1BS(60)

tuI ¦ % (60) (¼S 1

{%p0q F½r .hs½r  

A Sn1SMDA SnM M: D 3 / S: 79  

%

%( 2

%OPtuI¨ .v    ^5'70i HB2῍ 104 ῍

D0 $:u DS  80 120 (J/mol K)

L( &*Q H2O  NH3

  (Table 5)   

"1K :uM LMN

 !" 

 H3OS(H2O)n 2 NH4S(NH3)n -2~" 

# $



!"( H3OS  NH4S

! %& '# ()

DS  120 (J/mol K) BB- CI v :* %& +,- !" 


$ .

:u

K

M(

uH"*
Table 5 2'N H3OS (H2O)n /( - DS$n2

 80 (J/mol K) '01 (2 gO~"DHn1, nH>?@A n7K 

 3 !&58), 59)&~"  1 H2O$

PA  691 kJ/mol (Table 3) -2

 nx1, 2, 3,  

4" 256-789 :;<@Ag !" 837, 922, 997 kJ/mol 2g"=1!&-2 :789  >?@A (Table 5) nx1

< BC D"$ NH3$ E;!2

H2O

1H B IJ

E"!#FG$ -=1 ( PAPA >?

 [[837 kJ/mol

PAx854 kJ/mol ( B R5

* H3OS (H2O) )E;!#FG$

LMN789G-(B( (Table 3). R%&KLM)NOPK!Q' -2CNR H2O$ ( PA

1H( 789G $ H3OS

*T UHH V$WXGKBYZK)B 'N( +^:u (60) '~".6J¡

789GK &*Q +^:u

:H2O

!V$[@\@]()-+^ !789

H3OS(H2O)S(CH3)2COx[(CH3)2COSH2OSH]SSH2O -G$)*T,WXG" PA (_PQ [¢9 £¤- B 'N(+^:uIR

Table 3 3< M)*TUH

!V$WXGSTU-YBB %&V¤ !:u >"BB`789 =a -2B?@AA$ WG>?@A"¥¦ !K

-.b/" UH

H V$)*TWXSK - H3O 0cd1K H2O$e! - B &f   H3OS
(H2O)n2gK!>?@An3

h4(0 n i jk l5-=m6(- yf"§9( $:u-2 %&
X6
' B

>?@An7 ! R!&789 

0

:u

D

>@w;GDHn1, n nx4 -y o nx4 i 5<=->z{<-(( B! nx4 i 5 v"K"Z TorrCI

(H2O)n1(C2H5OH), YBR5-2 H%0 n 

$R5

$}

 B! n ( C2H5OH2S !\¬­® :&*[D 1 mTorr E%!"  H3OS(H2O)nn K

100°  300° H"±K % 100°\

(373 K) v H3OS  H3OS (H2O)

]

±K

 Table 5 R5 >z:u H3OSSH2O ῌ H3OS(H2O),

?-|G:u C2H5OH2S (H2O)n i H3OS
( 789>t@

m/z'N CI v"#ª

Q¯"!<789G&>t@ C2H5OH2S:uv" $¨Q M w 

 SMw "{< ! - $¨Q ©=Y«1-

-2R oK8 pq9Hrs
Table 5$J

DH v'²DS  ³146.3 kJ/mol v'² 126.2
K -2 DG xDH STDS x146,300

J/mol
373

126.2x99,227 J/molxRT

ln Kx8.31

373

ln

K B!'0 Kx8.0 1013 ( D0:uv>z'01 789>t@ $R5 $@0}~=Z K BC-´>z=ZµQ! ´C ^¶D

"AK H3OS ´ (atm)!NBC6#D(R5-2

¸- $Z;¹v"1

1NIH 8 t-C4H9S   :u-2 S

S:u EI7 t-C4H9 SH2O i t-C4H9OH2 -
789G& t-C4H9OH :t-t@< AK
Table 5 o1 ­·:u 'N :u _!"<=R5 nx1 i 2´

atm -`KB

- ´>z=Z K aº»( 1 mTorr
 10

3

/ 760 D´-2

S

I [H3O (H2O)]}/P(H2O)
S

- B



P(H2O)

K x { I [H3OS] /P(H2O) bcK!Q S] I [H3O ] : I [H3O (H2O)1]x1 : 1.1 108 ( de(7- F1#|G:u t-C4H9OH2 SH2O i±R5 H3OS(H2O)nH3OS(t-C4H9OH), YB0

H3OS (H2O) : H3OS (H2O)2 : H3OS (H2O)3 : H3OS (H2O)4 x1 :S t-C4H9OH  H  : u5 :uG KSn K \ H3OS :Y B  " H3O (H2O)n 

1.1 108 : 3.4 1013 : 8.5 1011 : 2.4 108 ( H%0

i-C4H8 :< AK B! D0-{< !

100°- H3OS(H2O)2 ´f6QgX B!

& ;I'[@@ H:u -2:u"h d¼'N(±CI '

Jv" y" A (S)nK
A 9@N S

S

300° (573 K)
S\ H3O : H3O (H2O) : H3OS

(H2O)2 : H3O (H2O)3 : H3OS (H2O)4 x1 : 7.4 : 3.41

103 :

1.9 108 : 4.6 1014 ( K(¹½ 100 i 300°

ῌ 105 ῌ

K. Hiraoka      H3O (H2O)n      H3OH3O  

(H2O)

 

  

 CI  !

U` $%&'" CI +a

8$%&%&'  :bIAucMq(0J: \+3 "Fde :  +f3(" (61)  163 kJ/mol " #

H3O NH3)NH4 H2O

0H# j:fTJ Li M rFb B C

3(

(61)

U g

 CI b:h $t` C iNL* {f~b C| : LiM$%&'"(

*" 163 kJ/mol +"  #

LF$ M L0 @A,kbO8(010 H2O 2 1.84 34

I- M X7 02\lm, - ./-5267&895 : - NH4 ;0 NH4 (H2O) <:n,A jS-:D-

4.

  =!( CI >?- :@ABCDEF?- 0G0GH#IA-"

4.1 

J /G KL$M

CI 

CI ?- X7

02

 Cl $%&%&':(IE ) 0N

H# JY " {$%&%&'| :(O *P+* <IQ R

(I-B:o-: (I, 0S-:(

TJ NO76).&/L0

1 "UVWV"# IQ @A2E
WX"+"3

CWX30), 31)":(IE

tDY"8k" :ue R,L0 1 ppm q\b[\]7[^_ [89 CL0`
 H3O(H2O)n  n ::;c JYvw¡C! PA : ¢AG, -1./

" AHB)ABH, _A/B)106, [BH]/[AH])0.01 {" AH  1£AJJ :H#IA[\]1,<d[=:>?

 @rb:p]

+*:Eq\"F R,rs?- 4

"5Y4Z "3569a&b#῏2"e <d@[=:"0 BH : "F| 200¤fgh&>:<IA 2iAj :BCA"xybzL MDG¥)RT¦ln K)8.31¦

jD [=: 10 K !]:O fgh

473¦ln10M2 ¦106 )36.2 kJ/mol&>EF:GIA|2::zc,JY(A fgh&>E: -2:H-
2I-k-0 ?l-:0m-D -mol¦K

:BpMq

1,(

L"0

A [=:JY N-rF1,\

S 0 OBCT

Q

xE4E

 ytb:zIA-

 !" CI 
" (45)  }0-rF:E 2 A1H q
B1HB2)B1B2H

b C|

A1 A2H)A1HA2

Li u FM :c1

0&b8k:

A st:(I-BC 02

01rF:E(45)

$%&'" \(IH :' "  ª L~(I #$%&
JY 9«' MY¬=!#:4E 

$%&'"?-8bIA "b ib 0­®0EE @4E:

Z uK[, W

$%&¢J2?-}0E rF Li +* M ;IQ LiM 0(42)

MjVWX

1,(2k-8MY(

8 36 kJ/mol

M0&b U n)1 ?-st 8(IE

kTO +*:q

" (42) }0-rF: B2H q : 

{Laval yt

Table 5 1, }b~Wu%L$BC" DY ¢AG , -4.2

CPvwQR30st  <I
G

1, 1 ppm  DG¥ῌDH¥E ¢AG , -OBst:<IAuE- &%¨zL DS¥῍0 J/

q\R, PA O8t

4:noOJ0 fgh&>E2KL
]:J

©

"{§

A\+ { ¯n| b 0/,AA]z0J °"±77), 78)

CE"



°±

-

Li  }b~W^E8 8st:² ³]´µ¶ 8(O °

(I- 4E2 _-rF<0 

± L"·=! 92NIQ
5

:

2 M

 LiM rFbK:( +E  +*9 L"¹%º¨h./ "F °±

8-rFb8k:0u- n 

6V/,A ¸b³  -²O8 °b±:(

῎ 106 ῎-²»3 B

Hunt ¼½3

79)

, “In

_z

the case of an exothermic gas phase proton transfer

B :; iQ .:; 1<reaction proceeding through a short-lived ion molecule13+ , 5d5E]P +@ F

complex, the energy liberated remains largely in theBQ / 7 GH*U9: +product containing the newly formed bond.” 

 

 

 (42)   B2H  B2H  !

/:  B  (45) 

 A1H  $%& '()./, )0;9+ , CI ';K 2(13: -LMNWOPpQP/, ) A2-  !"#

5d5#';F://yIJn7'"# $%& '() *+ , ) 

@U9:5

CI  112345

R`<) (10-5 Torr) '(EI) 



S

0B

8

BT4i EI B c5TU





'6 7

89 , )0 : ;.

VFc5`"W

9:<

=OH-  ;a/o0XYr/'I ,

8@'

!"#

:> '?) .

$%&

-

A2 C.

D n =G>  

EI  CI /'Z[ \ EI R`:AB)9 ,

4.3 

/i  _(<)`"W 1 EDFB

9:0B0]'K/5'%"\3 , P EI
8T)9  ^_r/i'U, )

 n (cm-3) !I3

 CI, ` APCI  aFT<

'GBT )Y =1 _`,nJkHn (s-1)

 1 Eb 1010 G> 5d5T)3

(62)

-3

)) B  n (cm ) KLMNO9 ,
-3

n (cm

18

)J 9.659H10 P (Torr)/T (K)=B / 

/}/}:/, )Yy a"; 19

#  1 RS:T> X& t (s) M (64) I3 ,c d 4 H 10s aYb 3 H 10

Torr  CI ,e s NO



0+U ms  )1

:

, 5

f-.g[E/X&23f-mn!0oY0+U7/0


:;



s6tuvw<,  x ms /y[E-PA Q EA 9/©.:; B'mjF

YhU9: PA == ¬­> 'U?opg,e~>'pI =7YjF 'mFi

wz 1 : ,  APCI 

CI {=:o:;Ui9, ppb U|}) ~>/ ppt):+@ V®
q:> :rs ¯ ,QBa°/ 

Qh±h'/ , T4t²

QBDFBe³´q'e³µT²3 (lD) /y,e³µT²3 lD `"W KLM¶O
9 ,lD (cm)J5/P (mTorr)
1 _` 1 Torr, 10:; ¬­> Q EA

4.4   f-.8[E9.: 

B [5¤¤1/ Fe¥fgh

'

_( 

[E34.: i

CL , q5 APCI  r`0
BG9.:h P 

f.g

Fi9 /yªn`9+ , « ''p

f.g[E34.: 5



|i., )0 jF `o0R/+@:h 1 ppm 5iijkl/, 3 

E-.dR'  F8¢FU£]P[E+ , I\ 1 ppm 5']^_(<)-5

B¡9c/() *ri9 *'k0 ,  ¨l(64)

# 2  1 Z'`* 5 Torr, aYb 760 Torr =1 _`> +@ t (s)-3[FU =+@Y ppt ¦§P> 'CY.

tJln 2/kῌnJ0.693/kῌn (s)t (s)  Y

89 , G() 

13

B()UB#VW$

%234 

'

(63)

P  (42) Q (45) A 1 RS:T





8


B k (cm3 /moleculeHs) B,  EI 

cm, 5H10-3-3

Torr a·(65)

lD  cd6H10-6

cm, aYb5 cm : , 1 mTorr `*_(us9 5 cm KL:  B2¸
YhU6vwF() Yy: ,_¹_(B b 400 m/s : c`*U?*:/, l _`L<)/@A/ B 1 Eb 1010, 107, 104 G'ºhxPP/V[E/B

/ , )Yy:fg_(0+ E '»p5d_`8C

D/  )  U ):3 _`LBG Torr  CI " 0+Yp¼y'\0+
5¤½¼y'

῍ 107 ῍

, ¼y'\K. Hiraoka  JK

 vd (drift velocity)    1,000 V/cm  *5 !

  !"#$%&
'"()*+,# 1"(-./ 0234 0 5

"KY.= (68) "$SF m<
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cmj3 >( 1 Torr

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PQ ArO  1 V/cm 

0J, 1 B Ar MN 1.63 cm/s "..#Torr

 !!R KEion  #$

 v d  "  $ Wannier  = . / S F:KEion<(1/2)mvd2O(1/2)Mbvd2O(3/2)kTZ&

60 K D

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WX":-">.  RB*#$Y(68)  m  !T# Mb MNT# k  T MND 0 = (68) U$

V WX  !"?
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 !,H, #$ !Y H
'(K $!LMN N2 zc¡!MNH$ 5 !

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  [\! 1 B 8 1,000 V/cm @&]P ?

= (66) ./^D)90#+;, I;+  !Y 

 vd 

 (3/2)kT YP$ , (1/2)mvd2

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 10 V/cm .& !!RV5"KK$ 5= (65)7 VW80), 81)Boltzmann

KY (62O62O621)I10j23 J+ DEF 300 K  360 K, >( 1 ? 
?

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f 

-

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1,800 cm/s  APCI  !_@$  !*: B

+H`./ !abNcdef g," 1 cm

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!!_-./hi 1/vd<5.6I!_T#;]^

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Y

!H

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V/cm 6uo

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῍ 108 ῍"m  ¼Z ½K$%

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    !"#$%&'())*+

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Keywords: Ion/molecule reaction, Proton transfer reaction,
Charge transfer reaction, Cluster ion, Negative ion

ῌ 110 ῌ