Professional Documents
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Review
Abstract
About ninety empirical functions for the representation of chromatographic peaks have been collected and tabulated. The
table, based on almost 200 references, reports for every function: (1) the most used name; (2) the most convenient equation,
with the existence intervals for the adjustable parameters and for the independent variable; (3) the applications; (4) the
mathematical properties, in relation to the possible applications. The list includes also equations originally proposed to
represent peaks obtained in other analytical techniques (e.g. in spectroscopy), which in many instances have proved useful in
representing chromatographic peaks as well; the built-in functions employed in some commercial peak-fitting software
packages were included, too. Some of the most important chromatographic functions, i.e. the Exponentially Modified
series and the Gram / Charlier series, have been reviewed and
Gaussian, the Poisson, the Log-normal, the Edgeworth / Cramer
commented in more detail. 2001 Elsevier Science B.V. All rights reserved
Keywords: Reviews; Mathematical functions; Chromatographic peaks
Contents
1. Introduction ............................................................................................................................................................................
2. Description of the table of the functions (Table 1) .....................................................................................................................
3. Remarks on some functions .....................................................................................................................................................
3.1. The EMG (Exponentially Modified Gaussian) ...................................................................................................................
3.2. The Poisson function.......................................................................................................................................................
3.3. The Log-normal function.................................................................................................................................................
series and the Gram / Charlier series..............................................................................................
3.4. The Edgeworth / Cramer
4. Commercial softwares .............................................................................................................................................................
5. Conclusions ............................................................................................................................................................................
References ..................................................................................................................................................................................
2
3
22
22
23
23
23
25
26
28
1. Introduction
It is well known that there is no theoretic model
for the exact description of the shape of chromatographic peaks. Several authors have proposed and / or
used a number of empirical mathematical functions
for the representation of these peaks [1,2,455,57
76,78114,116124,126148,150166,168190]. A
number of these functions have proved useful also to
represent the shape of signals obtained from other
analytical methods, as e.g. flow injection analysis,
various spectroscopic methods, voltammetry, mass
spectrometry, thermal analysis, etc.; conversely, several functions proposed for other techniques have
demonstrated suitable to represent chromatographic
peaks.
Perhaps the most frequent application of mathematical functions for peak shape representation is the
so-called deconvolution of partially resolved peaks
[4,610,1216,18,2325,29, 30, 39, 40, 44, 45, 48, 49,
54, 55, 57, 58, 61, 63 66, 68 70, 78, 80, 84 88, 95, 99,
103 105, 117, 126 128, 133, 137, 152 154, 156, 157,
159, 161, 163, 164, 166, 168, 171 174, 182, 189, 190]:
the analytical signal produced by the sum of n
partially overlapping peaks is reproduced by optimising (generally using the least squares criterion) the
parameters of the sum of n mathematical functions.
In this way the explicit expression of each of the n
functions is obtained, thus achieving an artificial
resolution of the n peaks. The potentialities and the
limits of this method have been extensively discussed by Maddams [116], Vandeginste and De
Galan [177] and, recently, by Zhang et al. [189]; in
the most recent applications the least-squares fitting
is combined with other mathematical methods of
data treatment (see e.g. [49,126,127,151,189]; although these papers deal mainly with spectroscopic
data, the methods described and the relevant conclusions are completely applicable to chromatographic
data as well).
Another important chromatographic application of
data fitting techniques (with or without peak deconvolution) is the computation of the so-called
chromatographic figures of merit (cfom) of peaks
[21, 26 28, 36, 41, 50, 52, 71 73, 89, 91, 96, 101, 118,
129, 130, 134, 135, 137, 138, 141, 144, 145, 150, 151,
166,169,175,178,186 188]. These include the first
statistical moments, which allow to calculate the
The first column of Table 1 contains the denomination proposed for each function, which generally
coincides with the one most frequently employed in
the literature; other denominations are reported in
brackets. For all the functions to which a specific
name (like Gaussian, EMG, Poisson, etc.) appears to
have not been assigned, we propose as the denomination the names of the Authors who, to our knowledge, have first proposed or used this function for the
representation of peaks. The same rule has been
followed in the cases in which the commonly used
denomination appears too generic and potentially
confusing (this is the case of names like skewed
gaussian, asymmetric gaussian, etc.).
For a few of the functions the commonly employed denomination appeared to be improper, because in mathematics it usually refers to a different
function; for example, this is the case of the Log-
y
t
(b) Parameters
It is advantageous to divide the adjustable parameters into two groups. The first group includes parameters which are directly correlated to one measurable
property of the experimental peak (like height,
width, retention time, etc.):
h
Table 1
List of the functions
Most used name/s
Baker (48 order
Lorentzian)
Beta
Equation
Cumulative
References
1
spectroscopy
? symmetric only
[9,10]
(rev. Maddams)
x2z
s 1 21
d sB 1 ]
w d
s 2 21
4
chromatography
spectroscopy
? single maximum
? tailed only
[111,125,167]
s2 2 1
B2 5 ]]
s1 1 s2 2 2
y 5 G(x)
y 5 G(x) 1 T(x)
y 5 G(x) 1 E(x)
for x , b
for b # x # c
for x . c
4
chromatography
? parameter z exact
? fronted, symm. or tailed
[26,129]
sx 2 zd 2
2 ]]
2w 2
constraints: a $ 0, c . b
F S
2, 3, 4
chromatography
? parameter z exact
? fronted, symm. or tailed
? stat. moments known
([130] exact, [27] approx.)
[27,76,125,130,145]
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[167]
7
chromatography
spectroscopy
? single maximum
? parameters z, s 1 , s 2 exact
? fronted, symm. or tailed
[167]
x2c
T(x) 5 asx 2 bd E(x) 5 asc 2 bd exp 2 ]
d
D G
H(x)
G(x) 1 1 2 ] E(x)
[27,76,125,130,145]
2
2
sx 2 zd
d
G(x) 5 exp 2 ]]
H(x) 5 1 2 tanh f asx 2 bdg E(x) 5 c exp 2 ]sux 2 eu 1 x 2 ed
2
2w 2
a
a
x2z1]
x2z2]
2
2
h 1 1 erf ]]
1 2 erf ]]
]
]
w 2
w2
y 5 ]]]]]]]]]]
2
a
1 1 erf ]
]
2w2
constraints: s . 0
[167]
y5h
F S DGF S DG
F S DG
Asymmetric
Cumulative
h
y5]
4
F S DGF S DG
w
x2z1]
2
]]
1 1 erf
]
s 12
constraints: s 1 , s 2 . 0
w
x2z2]
2
]]
1 2 erf
]
s 22
[167]
x2z
1 B 12s 2 B 1 ]
y 5 hB 12s
1
2
1
w
y50
G(x) 5 hexp
CheslerCram B
(GaussianHyperbolicExponential)
Properties
h
y 5 ]]]]]]
1 1 a(x 2 z)2 1 b(x 2 z)3 1 c(x 2 z)4
s1 2 1
B1 5 ]]
s1 1 s2 2 2
CheslerCram A
(GaussianTriangularExponential)
Applications
Table 1. Continued
Most used name/s Equation
p
x2z
y 5 hcos 2 ]s 1 (1 1 s)arctan ]
2
w
x2z
2 2(s11) / 2
s dgf1 1s]
w d g
y50
constraints: s . 2 1
12s
S 2 ]p2 ]
D1z
11s
p 12s
for x , w tanS 2 ] ]D 1 z
2 11s
for x $ w tan
x2z
F 2 ]12 s]
G
w d
Properties
References
7
spectroscopy
? single maximum
? parameter s exact
? fronted, symm. or tailed
[113]
Edgeworth
series
Cramer
y 5 hexp
H OH OH
n
s 21d
11
floor(i 12 / 2)
i51
s 21d
ic
i,i 12jsi12d!
j51
k50
x2z i 1222k
s 21d k ]
w
]]]]
k
2 k!si1222kd!
s d
GJJJ
2, 3
? fronted, symm. or tailed
chromatography ? stat. moments known
(see all references)
[3638,111,125,126,134137,155]
1, 2, 3, 4, 5
? single maximum
chromatography ? fronted, symm.a or tailed
FIA
? stat. moments known
voltammetry
[50,62,71,75,112,129,145,
186188]
[7,11,17,19,20,23,27,3235,42,43,4648,
50,51(and ref. therein),52,58,61,62,65,66,71,75,
81,89,90(and ref. therein),91-94,96,100,108,
110112,121,122,124,125,129,131,135137,139142,
145,146,154,156,160,162,167,173,183188 (rev. Maddams)]
7
? single maximum
chromatography ? fronted, symm.a or tailed
? stat. moments known
(the same of EMG)
[35,167]
s
a
a2
b
sa
s3
c 1,3 5 ], c 2,4 5 ], c 2,6 5 ], c 3,5 5 ], c 3,7 5 ], c 3,9 5 ], n538
6
24
72
120
144
1296
(for the other coefficients see [134])
floor(t)5the greatest integer #t,
[125,134]
EMG
(exponent.
modified
gaussian)
Generalized
EMG
hw
y5]
s
] 2 ]d GJ
2 ]D H1 2 erf F ]
]2 expS]
s
]2 s s
w
2s
]
p
w2
x2z
x2z
constraints: s . 0
hw
y5]
usu
] 2 ] ]D GJ
2 ]D H1 2 erf F ]
]2 expS]
s
]2 S usu
w usu
2s
]
p
w2
constraints: s 0
x2z
x2z s
Doniach
Sunjic
Applications
Table 1. Continued
Most used name/s
Simplified
EMG
Equation
Applications
w2 x 2 z
exp ]2 2 ]
s
hw ]
2s
y 5 ]2p ]]]]]]]
s
2.4055 x 2 z w
]]
]
1 1 exp 2
2]
]2
w
s
dG
References
7
chromatography
? single maximum
? fronted, symm.a or tailed
? stat. moments known
(practically the same of
EMG in the range
s/w50.7543 [110])
[110]
7
chromatography
? single maximum
? fronted, symm.a or tailed
? stat. moments known
(practically the same of
EMG in the range
s/w 5 0.75 4 3 [110])
[110]
constraints: s . 0
Second
simplified
EMG
Two time-constants
EMG
S
S
D
D
]
p
w2 x 2 z
] exp ]2 2 ]
2
s
2s
3.3382
12exp 2 ]
C(x)
]2
3 11 ]]]]h120.3328 exph20.61025[C(x)] 2 jj
3.3382
11exp 2 ]
C(x)
]2
x2z w
C(x) 5 ] 2 ]
w
s
constraints: s . 0
hw
y5]
s
]
hw
p
y 5 ]] ] f Dss 1d 2 Dss 2d g
s1 2 s2 2
hw 2
y5]
2
s1
H F
S
exp
w2 x 2 z
Dssd 5 exp ]2 2 ]
s
2s
constraints: s 1 , s 2 . 0
]
p
1 ]Css 1dDss 1d
2
1 2 erf
Cssd
2]
]2
[110]
[110]
if s 1 s 2
G
J
DH F GJ
sx 2 zd 2
2 ]]
2
2w
6
if s 1 5 s 2
x2z w
C(s) 5 ] 2 ]
w
s
7
chromatography
? single maximum
? symm.a or tailed only
? stat. moment zero (area)
known (the same of EMG)
[35]
Properties
Equation
Generalized
two time-constants
EMG
]
hw
p
y 5 ]] ] f Dss 1d 2 Dss 2d g
s1 2 s2 2
]
hw 2
sx 2 zd 2
p
y5]
exp 2 ]]
1 ]Css 1dDss 1d
2
2
2
s1
2w
Applications
H F
S
G
J
DH F GJ
s
w2 x 2 z
Dssd 5 ] exp ]2 2 ]
s
usu
2s
constraints: s 1 , s 2 0
Three time-constants
EMG
if s 1 s 2
hw]
p
y 5 ]]
T Dss d 1 T 2 Dss 2d 1 T 3 Dss 3d g
]2 f 1 1
]
h
w2
p
sx 2 zd 2
]Css 2dDss 2d 1 exp 2 ]]
y 5 ]] ]
2
s2 2 s1 s2
2
2w
H H
s1w ]
p
2 ]] ]sDss 1d 2 Dss 2dd
s1 2 s2 2
(this equation is valid for s 1 5 s 2 . For s 1 5 s 3 and for s 2 5 s 3 simply substitute the given si [35])
H F
JJ
]
]
p
sx 2 zd 2
p
]Dss 1d 1 Css 1d exp 2 ]]
1 Css 1d ]Dss 1d
2
2
2
2w
s1
s2
s3
T 1 5 ]]]] T 2 5 ]]]] T 3 5 ]]]]
ss 2 2 s 1dss 3 2 s 1d
ss 1 2 s 2dss 3 2 s 2d
ss 1 2 s 3dss 2 2 s 3d
3
hw
y5]
3
2s 1
w2 x 2 z
Dssd 5 exp ]2 2 ]
s
2s
DH F
1 2 erf
Cssd
2]
2]
GJ
7
chromatography
? single maximum
? fronted, symm.a or tailed
? stat. moment zero (area) known
(the same of EMG)
[35]
7
chromatography
? single maximum
? symm.a or tailed only
? stat. moment zero (area)
known (the same of EMG)
[35]
x2z w
C(s) 5 ] 2 ]
w
s
if all si differ
GJ
References
if s 1 5 s 2
Cssd s
]
2]
]2 usu
1 2 erf
Properties
Table 1. Continued
x2z w
Cssd 5 ] 2 ]
w
s
constraints: s 1 , s 2 , s 3 . 0
Table 1. Continued
Equation
Applications
Generalized
three time-constants
EMG
hw]
p
y 5 ]]
T Dss d 1 T 2 Dss 2d 1 T 3 Dss 3d g
]2 f 1 1
]
h
w2
p
sx 2 zd 2
]Css 2dDss 2d 1 exp 2 ]]
y 5 ]] ]
2
s2 2 s1 s2
2
2w
H H
if all si differ
GJ
s1w
2 ]]
s1 2 s2
]
p
] f Dss 1d 2 Dss 2d g
2
Properties
References
7
chromatography
?
?
?
?
[35]
7
chromatography
? single maximum
? fronted, symm. or tailed
(this equation is valid for s 1 5 s 2 . For s 1 5 s 3 and for s 2 5 s 3 simply substitute the given si [35])
H F
JJ
]
]
p
sx 2 zd 2
p
]Dss 1d 1 Css 1d exp 2 ]]
1 Css 1d ]Dss 1d
2
2
2
2w
s1
s2
s3
]]]]
]]]]
]]]]
T1 5
T 5
T 5
ss 2 2 s 1dss 3 2 s 1d 2 ss 1 2 s 2dss 3 2 s 2d 3 ss 1 2 s 3dss 2 2 s 3d
s
w2 x 2 z
Cssd s
x2z w
]
Dssd 5 ] exp ]2 2 ]
1 2 erf 2 ]
Cssd 5 ] 2 ]
s
2] usu
w
s
usu
2s
3
hw
y5]
3
2s 1
DH F
single maximum
all parameters estimable
fronted, symm.a or tailed
stat. moment zero (area)
known (the same of EMG)
GJ
constraints: s 1 , s 2 , s 3 0
S
F
DF S
GH F
2
2s 1 z 2 2s 1 x 1 w
h
] exp ]]]
4s 1
s 21
EMG1GMG
y5
Ef
`
y5h
DG
GJ
s 2sz 2 xd
2 ]]
1 2 erf ]]]
]]
2(w 2 1 s 22 )
w 2(w 2 1 s 22 )
1 ]]]]]]]]]]
] ]]
22pw 2 1 s 22
h exp
sx 2 zd 2
constraints: s 1 . 0
EML
(exponent
modified
lorentzian)
s1z 2 s1x 1 w
1 2 erf ]]]
]
ws 12
x2z2t
1 1 ]]
w
[167]
[167]
2 21
dg
t
exp 2 ] dt
s
s d
[42]
4
chromatography
properties unknown
[42]
Table 1. Continued
Equation
Applications
Erf
y 5 h 1 2 erf
Error
y 5 hexp
x2z
ux 2 zu 2 / a
2 ]]
2w
[167]
G
[167]
Extreme
value
fronted
x2z
x2z
y 5 hexp 2 exp 2 ] 2 ] 1 1
w
w
y 5 hexp
Fahys
y 5 hexp
x2z
y 5 h cos p ]
w
DG
dg
? single maximum
? parameters h, z, w exact
? symmetric only
[167]
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[167]
4
chromatography
? single maximum
? parameters h, z, w exact
? tailed only
[111,125,167]
7
chromatography
? single maximum
? parameters h, z, s exact
? fronted or symm only.
[167]
7
chromatography
? single maximum
? parameters h, z, s exact
? symm. or tailed only
[167]
1
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[44]
(rev. Maddams)
1
spectroscopy
? single maximum
? fronted, symm. or tailed
[44]
(rev. Maddams)
[167]
a
b
]]]
b 2 1 (x 2 z)2
w
w
for z 1 s 2 ] # x # z 1 s 1 ]
2
2
w
w
for x , z 1 s 2 ] and for x . z 1 s 1 ]
2
2
[44]
constraints: a . 0, b 0
x2z2s
y 5 h cos p ]]
w
f s
7
chromatography
spectroscopy
[167]
x 2 z 1 w ln s
2 x 1 z 1 w 2 wzexp 2 ]]]
w
]]]]]]]]
ws
y50
Asymmetric
Fahys
[111,125,167]
DG
constraints: s . 0
f s
x 2 z 2 w ln s
x 2 z 1 w 2 wzexp ]]]
w
]]]]]]]
ws
constraints: s . 0
Extreme
value
tailed
References
fs]
w d gj
constraints: a . 0
Extreme
value
(extreme function in statistics)
Properties
b2
dg ]]]
b 1 (x 2 z)
y50
constraints: a . 0, b 0
w
w
for z 1 s 2 ] # x # z 1 s 1 ]
2
2
w
w
for x , z 1 s 2 ] and for x . z 1 s 1 ]
2
2
[44]
10
Table 1. Continued
Most used name/s
F-variance
Equation
Applications
constraints: s 1 $ 2, s 2 . 0
y5h
x2z
s211]
w
2 ]]]
s21
[167]
4
chromatography
? single maximum
? parameters h, z exact
? symm.a or tailed only
[111,167]
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? symm.(a) or tailed only
167
1, 2, 3, 4, 5, 6
chromatography
FIA
spectroscopy
voltammetry
mass spectrom.
? single maximum
? parameters h, z, w exact
? symmetric only
? stat. moments known
(see e.g. [144])
[1,4,5,7,8,12,1315,22,2426,
28,29,32,41,43,45,46,52,5456,
58,61,63,67,6870,84,88,97,98,
100,103,105107,109,120,122,
124128,131,133,135139,144,
146,147,151,152,154,156162,
166171,182 (rev. Maddams)]
[167]
x2z
exp 2 ]
w
for x $ w 1 zsw
for x , w 1 zsw
[111,167]
sx 1 x 1 w 2 zs 2 z 2s
sx 2 zdss 1 1d 2
hw ]]]]
exp ]]]]
w
sx 1 x 1 w 2 zs 2 z
y 5 ]]]]]]]]]]]
sx 1 x 1 w 2 zs 2 z
y50
constraints: s . 0
Gaussian
? single maximum
? parameters h, z exact
? symm.a or tailed only
s21
y50
constraints: s . 1
Inverted Gamma
7
chromatography
spectroscopy
s 2ss 1 2 2d
for x , z 2 w ]]
s 1ss 2 1 2d
y50
Gamma
(Chisquared)
s 2ss 1 2 2d
for x $ z 2 w ]]
s 1ss 2 1 2d
References
y 5 hexp
sx 2 zd 2
2 ]]
2w 2
z 1 sz 2 w
for x $ ]]
s11
z 1 sz 2 w
for x , ]]
s11
[167]
[8,12,46,61,69,
105,106,120,122,
125,138,146,156,
157,160,162,167,
169,182]
s 1 2 2 (s 1 1s 2 ) / 2
x 2 z s 2ss 1 2 2d (s 1 1s 2 ) / 2
h ] 1 ]]
11]
w
s 1ss 2 1 2d
s2 1 2
y 5 ]]]]]]]]]]]]
s 1 1s 2 / 2
x 2 z s 2ss 1 2 2d
s 1 ] 1 ]]
w
s 1ss 2 1 2d
s 2ss 1 2 2d s 1 / 221
]]
1 1 ]]]]]
s2
s 1ss 2 1 2d
Properties
Table 1. Continued
Most used name/s
Equation
bi-Gaussian
y 5 hexp
Constrained
Gaussian
Double
Gaussian
y 5 hexp
F
F
sx 2 zd 2
2 ]]
2w 21
sx 2 zd 2
2 ]]
2w 22
G
G
F S
1
x2z
2 ] ]]
2 zw 2 1 w 1
h
y5]
]
2p
for x , z
for x $ z
[74,97,108,145,182]
DG
[167]
1 x 2 z1
2] ]
2
w1
s1 2 ad
1 ]] exp
w2
F S D GJ
1 x 2 z2
2] ]
2
w2
constraints: 1 # a # 0
GEMG4
(4-parameter
EMG-GMG hybrid)
GEMG5
(5-parameter
EMG-GMG hybrid)
GH
F
D
h
y 5 ]]]]]]
exp
]2s 1
]]
2
2
]
2
p
(s
1
w
)
erf
2
1
1
2s 2
H F
2 1 1 erf
s 1ss 2 x 2 zs 2 2 w 2d
]]]]
]]
ws 22(s 21 1 w 2 )
ss 2 x 2 zs 2 1 s 12d2
2 ]]]
2s 22 (s 21 1 w 2 )
[21,63,74,97,108,141,145,146,
164,182]
(rev. Maddams)
single maximum
parameters h, z, w 1 , w 2 exact
fronted, symm. or tailed
stat. moments known
[21,74,145]
? single maximum
? parameters h, z exact
? symmetric only
[167]
2
chromatography
? parameters z 1 , z 2 exact
? fronted, symm. or tailed
[141]
7
chromatography
? single maximum
? fronted, symm. or tailed
[167]
7
chromatography
? single maximum
? fronted, symm. or tailed
[167]
1, 2, 3
chromatography
? single maximum
? parameters h, z exact
? fronted, symm.a or tailed
? stat. moments known [83,175]
[83,174,175]
7
spectroscopy
G
[167]
x2u
H f s d 1 a lns]
J
z 2 u dg
b21
x2u
y 5 hexp ] 1 2 ]
a
z2u
y50
constraints: a . 0, b . 1
[167]
GJ
constraints: s 2 0
GEX
(generalized
exponential
function)
GJ
S D
?
?
?
?
[141]
2
sx 2 z 1 sd 2
w 2 ssx 2 zd
2 ]]
2 1 1 erf ]]]
]]
2(s 2 1 w 2 )
w2(s 2 1 w 2 )
y 5 ]]]]]]]]]]]
]
2
]]
21
2p (s 2 1 w 2 ) erf ]
2
h exp
References
H F S DG
a
] exp
w1
1, 2, 4
chromatography
spectroscopy
Properties
y 5 hexp
Applications
for x $ u
for x , u
[83,174,175]
11
12
Table 1. Continued
Most used name/s
Equation
Giddings
h
y5]
w
Applications
]z
2]
zx
DGI S]
D
]x FexpS 2 ]
w
w
1
t
I std 5 O ]]s]d
5modified Bessel function of the first kind
k!sk 1 1d! 2
x1z
2k11
y 5 hexp
k50
sx 2 zd 2
2 ]]]
2
2w 1 ssx 2 zd
7
? single maximum
[61]
chromatography ? parameters h, z, s exact
for x # z 2 2w 2 /s (if s . 0) or x $ z 2 2w 2 /s (if s , 0) [61]
? fronted, symm. or tailed
sx 2 ud 2
2 ]]
2w 2
GH F
GJ
sx 2 zd 2
ssx 2 zd
h exp 2 ]]
1 1 erf ]]]
]]
GMG
2ss 2 1 w 2d
w2ss 2 1 w 2d
(half-gauss.
y 5 ]]]]]]]]]]]
]]
2pss 2 1 w 2d
modified gaussian.)
Gram
Charlier series
y 5 hexp
F s d GO
1 x2z
2] ]
2 w
n
i50
s 2 1d
ic
for x , u
7
? single maximum
chromatography ? parameter u exact
? tailed only
[167]
7
? single maximum
[167]
chromatography ? fronted, symm. or tailed
for x $ u
y50
constraints: a . 0, b . 0
floorsi / 2d
j50
x 2 z i22j
s 2 1d j ]
w
]]]]
2 j j!si 2 2jd!
s d
GJ
n 5 38
Haldna
Pihl
y 5 hexp
y50
[37,38,59,60,65,
76,92,111,119,
125,167,178]
y50
Gladney
Dowden B
4
? single maximum
chromatography ? only symm.a or tailed
References
sx 2 zd 2
2 ]]]]]]]
s
w 1 ]sx 2 zd h1 1 tanh f 1000sx 2 zd g j
2
always (if s . 0)
for atanh(21 2 2w/s) , x , z 2 2w/s (if s , 0)
for x # atanh(21 2 2w/s) and for x $ z 2 2w/s (if s , 0)
[80]
[61]
1, 2, 3
? parameter w exact
[36,72,73,119,
chromatography ? for n$3 fronted,
123,125,130,133,
symmetric or tailed,
137,178]
for n , 3 symmetric only
? stat. moments known
(see all references)
1
? single maximum
[80]
Chromatography ? parameters h, z exact
? fronted, symm. or tailed
Gladney
Dowden A
[65,111,125,167]
Properties
Table 1. Continued
Most used name/s
HVL
(Haarhoff
Van der Linde)
Koskelo
(modified
gaussian)
Applications
Laplace
(double exp.)
Levy
Martin
[65,167]
1, 2, 4
chromatography
? single maximum
? fronted, symm.a or tailed
? stat. moment zero
(area) known [145]
[65,79,92,111,
136,145,167]
for x $ u
for x , u
[167]
7
chromatography
spectroscopy
? single maximum
? parameter u exact
? tailed only
[167]
1, 2
spectroscopy
? single maximum
? parameters h, z, s 1 , s 2 exact
? fronted, symm. or tailed
[101,180]
7
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[102]
7
spectroscopy
? single maximum
? parameters h, z, w exact
? symmetric only
[167]
1
chromatography
voltammetry
? single maximum
? parameters h, z, s exact
? fronted, symm. or tailed
[78,172,173]
7
chromatography
? single maximum
? parameters h, z, w exact
? symmetric only
[111]
F S D G
F
F
F
y 5 hexp
y 5 hexp
2x 2 2z 1 s 21
s 21 ]]
2
2w
sx 2 zd 2
2 ]]
2
2w
2z
2
2x
1 s 22
s 22 ]]
2
2w
x2z
y 5 h sech ]
w
f s dg
DG
for x , z 2 s 21
for z 2 s 21 xz 1 s 22
for x . z 1 s 22
[167]
sx 2 zd 2
2 ]]]
2 f w 1 ssx 2 zdg 2
h[2exps 2 2d 1 1]
y 5 ]]]]]]]]
z2w2x
x2z2w
exp 2 ]] 1 exp 2 ]] 1 1
w
w
[101]
constraints: a . 0
]2ux 2 zu
y 5 hexp 2 ]]
w
y 5 hexp
F S
y50
for x # z 2 w/s (if s $ 0) or for x $ z 2 w/s (if s , 0) [78]
(this function can be considered a simplified TorresLapasio function. It has been
used as the first part of a linear combination to represent polarographic peaks)
Li A
References
sx 2 zd 2
exp 2 ]]
2
hw
2w
y 5 ]]
] ]]]]]]]]]]
21
zs
1
1 x2z
zs2p
]
exp ]2 2 1
1 ] 1 1 erf ]
2
2] w
w
y 5 hexp
Kowalski
Isenhour
Properties
Intermediate
Equation
13
14
Table 1. Continued
Most used name/s
Li B
Li C
Applications
Asymmetric
Logistic
(logistic power)
Log-normal
(skewed
gaussian)
(Fraser-Suzuki)
3 parameters
Log-normal
References
7
chromatography
? single maximum
? fronted, symm. or tailed
[111]
7
chromatography
? single maximum
? fronted, symm. or tailed
[111]
1
chromatography
? parameter w exact
? tailed only
[69,70,133,136]
? single maximum
? parameters h, z, w exact
? symmetric only
? stat. moment zero (area) known [84]
[43,84,125,167]
? single maximum
? parameters h, z, w, s exact
? fronted, symm. or tailed
[167]
[167]
7
chromatography
spectroscopy
wr sr
for x . z 2 ]
s r2 2 1
wr sr
for x # z 2 ]
s 2r 2 1
1, 2, 4
chromatography
FIA
spectroscopy
?
?
?
?
[8,55,56,58,6971,92,
109,111,133,135137,145,
152,163165,167,185]
7
chromatography
spectroscopy
? single maximum
? tailed only
h
y 5 ]]]]]]]]]]]
z 2 w 2 x a2
x 2 z 2 w b2
1 1 a 1 exp ]]
1 1 1 b 1 exp ]]
21
w
w
constraints: a 1 , a 2 , b 1 , b 2 . 0
[111]
h
y 5 ]]]]]]]]]]]]]]
z 2 w 2 x s(z2w) / xda 2
x 2 z 2 w sx / (z1w)db 2
1 1 a 1 exp ]]
1 1 1 a 2 exp ]]
21
w
w
constraints: a 1 , a 2 , b 1 , b 2 . 0
[111]
]z
2z
y 5 h ] exp 2 ]2 s]z 2]xd 2
for x . 0
x
w
dg f
dg
dg
dg
y50
Logistic
(theorical
voltammetric
peak)
Properties
for x # 0
[69]
x2z
4exp 2 ]
w
y 5 h ]]]]
x2z 2
1 1 exp 2 ]
w
s
s
y5h
d
dg
11exp
[125,167]
x1w ln(s)2z
2 ]]]
w
DG
2s21
constraints: s . 0
y 5 hexp
ln r
2 ]]
sln srd 2
HF
ln
sx 2 zdss r 2 1d
]]] 1 1
wr sr
GJ J
2
x1w ln(s)2z
2 ]]]
w
y50
constraints: sr . 0,sr 1,1 , r , `
[56 (r52), 58 (r52), 69 (r52), 71,111,135,137,165 (r52), 167 (r52)]
h
y 5 ]]
] exp
wx2p
x
ln 2 ]
z
2 ]]
2w 2
sd
[125]
1, 5
spectroscopy
voltammetry
single maximum
parameters h, z, w, sr exact
fronted, symm.a or tailed
stat. moments known [71,135,145]
[125,167]
Littlewood
Equation
Table 1. Continued
Equation
Lorentzian
(Cauchy)
h
y 5 ]]]
x2z 2
114 ]
w
LorenzianGaussian
product
sx 2 zd 2
exp 2s1 2 ad]]
2w 2
y 5 h ]]]]]
(x 2 z)2
1 1 a ]]
2
constraints: 0 # a #w1
Asymmetric
LorenzianGaussian
product
Applications
[2,5,39,40,5456,84,
99,107,109,128,146]
s d
JJ
2
12a
x2z
exp 2 ] ]]]
2
w f 1 1 s(x 2 z) g
y 5 h ]]]]]]]
2
x2z
1 1 a ]]]
w f 1 1 s(x 2 z) g
Asymmetric
LorenzianGaussian
sum
(linear combination)
(Pseudo Voigt 2)
H
H
y5h
a exp
a exp
sx 2 zd 2
2 4 ln 2 ]]
2
w
ln
12a
1 ]]]
sx 2 zd 2
1 1 4]]
w2
2ssx2zd
]]11
w
12a
1]]]]]]
2
2ssx2zd
ln ]]11
w
11]]]]]
s2
y50
constraints: s 0, 0 # a # 1
FS
[1,2,4,5,25,3941,43,5356,
58,68,84,87,88,95,99,107,
109,113,125,128,144,146148,
151,152,158,161,167169,189]
(rev. Maddams)
1, 2, 3
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[1,49,64,68,113,147,148,150,167]
(rev. Maddams)
7
spectroscopy
? single maximum
? parameters h, z exact
? fronted, symm. or tailed
[113]
1, 2, 5
spectroscopy
voltammetry
? single maximum
? parameters h, z exact
? symmetric only
[13,43,49,5557,63,64,117,118,
125,143,147,148,150,152,167,
169,171,176,177] (rev. Maddams)
? single maximum
? parameters h, z exact
? fronted, symm. or tailed
[18,39,55,125]
[5557,150]
H FS
ln 2
2]
s2
? single maximum
? parameters h, z, w exact
? symmetric only
1, 2, 3, 4, 5
chromatography
spectroscopy
voltammetry
mass spectrom.
constraints: 0 # a # 1
y5h
References
[167]
y50
constraints: 0 # a # 1
LorenzianGaussian
sum
(linear combination)
(Pseudo Voigt 1)
Properties
DG
DG J
2
[18,55]
1
chromatography
spectroscopy
voltammetry
15
16
Table 1. Continued
Most used name/s
Equation
bi-LorenzianGaussian sum
y5h
y5h
Applications
H F
H F
a exp
sx 2 zd 2
2 ]]
2w 21
b exp
sx 2 zd 2
2 ]]
2w 22
G
G
1s1 2 ad
1s1 2 bd
F
F
sx 2 zd 2
1 1 ]]
w 21
sx 2 zd 2
1 1 ]]
w 22
GJ
GJ
Losev B
2, 4
chromatography
? single maximum
? parameters h, z, w 1 , w 2 exact
? fronted, symm. or tailed
[145]
4
chromatography
? single maximum
? parameters h, z, w 1 , w 2 exact
? fronted or tailed only
[108]
7
spectroscopy
?
?
?
?
[113,114]
7
spectroscopy
? single maximum
? parameters w 1 , w 2 exact
? fronted, symm. or tailed
[113]
[65,111]
1, 4
chromatography
? single maximum
? fronted, symm. or tailed
[65,91,111,167,181]
for zw # x # z 1 w
4
chromatography
spectroscopy
? single maximum
? parameters h, z, w exact
? symmetric only
[53,146,169]
for x , z
21
for x $ z
[145]
for x , z
F S DG
for x $ z
sx 2 zd 2
2 ]]
2w 21
x 2 z 2 21
y5h 11 ]
w2
h
y 5 ]]]]]]
x2z
x2z
exp 2 ] 1 exp ]
w1
w2
y 5 hexp
D S D
h
y 5 ]]]]]]]
a
x2z
x2z
exp 2 ] 1 exp ]
w1
w2
F S
D S DG
constraints: a . 0
NLC
(Non-linear
chromatogr.)
]z
]
2zx
Dexps]]
]x I S]
w
w d
s dg ]]]]]]
s
z x
1 2 1 2 exp 2 ] T ],]
h
s
y 5 ] 1 2 exp 2 ]
ws
w
2x2z
Tsr,vd 5 exps 2 vd
s w dg s w w d
single maximum
parameters w 1 , w 2 exact
fronted, symm. or tailed
stat. moments known [114]
]
exps 2 tdI0s2vtd dt
Instd 5
Parabola
1
t
]
k!sk 1 nd! 2
k50 ]]
x2z
y5h 12 ]
w
2k1n
f s dg
y50
sd
Losev A
References
21
contraints: 0 # a # 1, 0 # b # 1
Mixed Lorentzian2Gaussian
Properties
Table 1. Continued
Most used name/s
Pearson IV
Equation
Applications
constraints: s 1 . 0
Pearson IVa
hs
y 5 ] exp
w
s tan
ws
x1]2z
2
]]
w
DG F
2
ws
x1]2z
2
]]]
11
w2
constraints: s 0
Pearson IVb
hs
sp
y 5 ] exp ] s4 1 s 2d exp
2w
2
F S
s tan
21
ws
x1]2z
4
]]
w
DG F
constraints: s 0
Asymmetric
Pearson VII
(asymmetric
Fraser Suzuki)
x2z
y5h 114 ]
w
? single maximum
? parameters h, z exact
? fronted, symm. or tailed
[167]
Gf
21
sp
sp
exp ] 2 exp 2 ]
2
2
s d
s dg
21
7
chromatography
spectroscopy
? single maximum
? parameters z, s exact
? fronted, symm.a or tailed
[167]
ws
sx 1 ]4 2 zd
1 1 ]]]
w2
22
sexpsspd 2 1d 21
7
chromatography
spectroscopy
? single maximum
? parameters z, s exact
? fronted, symm.a or tailed
[167]
1
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
? stat. moment zero (area) known [55,84]
[30,55,56,84,125,167,169]
(rev. Maddams)
1
spectroscopy
? single maximum
? parameters h, z exact
? fronted, symm.a or tailed
[55]
(rev. Maddams)
[167]
2
f s d s2
1/a
2 1d
2a
constraints: a . 0
[30,56,84,167]
h
y 5 ]]]]]]]]]
a2
a 22
2
2s(x 2 z)
2 21
]]
1 1 ]]
ln
1
1
w
s2
7
chromatography
spectroscopy
[167]
s d
Pearson VII
(Fraser
Suzuki)
References
[167]
F S
21
Properties
HF
y50
]
constraints: 0 , a ,2, s 0
GJ J
H F S D S DGJ
S D F S DG
ws 2
x2]2z
2s 1
s2
y 5 h exp 2 s 2 tan 21 ]]
1 tan 21 ]
2
2s 1
w
2s 1
2
ws 2
x2]2z
s1
s 22
2s 1
3 1 1 ]2
1 1 ]]]
4s 1
w2
17
18
Table 1. Continued
Most used name/s
Equation
Poisson
(Gamma)
(MartinSinge)
x
x
y 5 hexp s1 2 ad ] 2 ln ] 2 1
z
z
y50
constraints: a . 1
s d gj
d s
d s
x2u
y 5 4h exp 2 ]
w
x2u
df1 2 exps 2 ]
w dg
[125]
? single maximum
? parameters u, w exact
? tailed only
[167]
[167]
7
chromatography
spectroscopy
x2u
df1 2 exps 2 ]
w dg
? single maximum
? parameter w exact
? tailed only
[125,167]
[125]
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? fronted or tailed only
[113,150]
? single maximum
? tailed only
[167]
for x $ u
for x , u
s1 2 cd d
2ux 2 zu]]
ce
2
spectroscopy
Tsxd 5 0
constraints: 0 # b # 1, c(0.3, d(1, e(0.2
Symmetric
double
Sigmoid
? single maximum
? parameters h, z exact
? symmetric only
for x $ u
y50
Sherwood
7
spectroscopy
[125]
for x , u
x2u
y 5 h exp 2 ]
w
[21,31,37,69,70,74,
111,133,136,137,
146,154,178,184]
6 21
y50
Pulse with
power term
? single maximum
? parameters h, z exact
? tailed only
? stat. moments known [74]
1, 2, 4
chromatography
dg
constraints: a . 0, b . 0, c . 0
Pulse
References
for x $ 0
for x , 0
[69]
x2z 2
x2z 4
x2z
y 5 h 1 1 a 2] 1 b 2] 1 c 2]
w
w
w
f s
Properties
w
w
x2z
h 1 1 exp 2 ]
1 1 exp ] exp 2 ]
2s
2s
w
y 5 ]]]]]]]]]]]
w
w
x2z1]
x2z2]
2
2
1 1 exp 2 ]]
1 1 exp 2 ]]
s
s
F S
s dgf
s dg s
DGF S
DG
[167]
7
chromatography
spectroscopy
Inverse
Polynomial
Applications
Table 1. Continued
Most used name/s
Square Sine
y5h
Applications
F S
1 1 exp
w
x2z1]
2
]]
2
s1
p x2u
y 5 h sin ] ]
2 z2u
f s
dg
DG H F S
21
12
Student t
[128]
h
y 5 ]]]]]]
sx 2 zd 2 s(s / 2)1(1 / 2)d
1 1 ]]
sw 2
constraints: s . 0
TorresLapasio
[125,167]
y 5 h exp
? single maximum
? fronted, symm. or tailed
[125,167]
4
spectroscopy
? single maximum
? parameters h, z, u exact
? symmetric only
[53,125,169]
1
spectroscopy
? single maximum
? parameters h, z, w exact
? symmetric only
[9,10,128]
(rev. Maddams)
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? symmetric only
[167]
4
chromatography
[172,173]
7
chromatography
spectroscopy
21
for u # x # 2z 2 u
h
y 5 ]]]]2
sx 2 zd 2
1 1 4]]
w2
DG J
References
y50
constraints: z . u
Student
(48 order
Lorentzian)
1 1 exp
w
x2z2]
2
]]
2
s2
Properties
[167]
sx 2 zd 2
2 ]]]]]
2 f w 1 o ni51 sisx 2 zd i g 2
[172]
Asymmetric
double
Sigmoid
Equation
19
20
Table 1. Continued
Most used name/s
Equation
Applications
Triangle
ux 2 zu
y5h 12]
w
for z 2 w # x # z 1 w
y50
Voigt
(GaussianLorentzian convolut.)
y5h
x2z
x2z
a exp 2 ln 2 ] 2 s ]
w
w
constraints: 0 # a # 1
]
`
2h2
y 5 ]]
]3 2` exp
w 1 w 2 3p
12a
u g j 1 ]]]]
x2z
x2z
1 1 f ] 2 su]u g
w
w
2
References
4
chromatography
spectroscopy
? single maximum
? parameters h, z, w exact
? symmetric only
[53,146,169]
7
spectroscopy
? single maximum
? parameters h, z, s exact
? fronted, symm. or tailed
[176]
(rev. Maddams)
1, 3
spectroscopy
? single maximum
? parameter z exact
? symmetric only
1
chromatography
? single maximum
? parameters h, z, u exact
? fronted, symm.a or tailed
? stat. moments known (see GEX)
[69,70,133,136,137,167]
7
chromatography
spectroscopy
? single maximum
? parameters h, z exact
? fronted, symm.a or tailed
[125,167]
[176]
F S D G F S DG
t2z
22 ]
w1
4 x2t
11] ]
3
w2
a21
x2u
x2u
1 2 ] 1 a lns] dg J
H]
a f sz 2 ud
z2u
21
dt
[143]
Weibull
y 5 h exp
y50
constraints: a . 1
Weibull 3
(Weibull)
1/a
(12a) / a
1/a
y50
for x # u
[69]
x2z
a21
1S]D G
S D F]
w
a
x2z
a21
a21
3exp H 2 F ] 1S] D G 1 ] J
w
a
a
a21
y5h ]
a
for x . u
a21
S D
1/a
S D
1/a
a21
for x . z 2 ]
a
a21
for x # z 2 ]
a
[125,167]
V. Haverbeke
Brown
for x . z 1 w or x , z 2 w
[146]
Properties
All the parameters quoted above (with the exception of s) are always positive for positive peaks,
like those usually encountered in chromatography.
Negative peaks can be fitted simply by changing the
sign of the appropriate parameter.
The second group includes parameters which
(usually) cannot be directly correlated to a measurable property of the experimental peak, and often
affect the peak shape in a complex way. The value of
this kind of parameters (which have been indicated
with lower-case letters, a, b, etc.) is generally
difficult to estimate; this fact can negatively affect
the convergence of a least-squares non-linear fitting
algorithm to the true minimum [149]. In addition,
parameters of this kind are often strongly correlated
to one or more of the other ones, thus further
21
DG S
F S
(1)
(2)
S D
(3)
(4)
22
E f(x, h, z, . . . ) dx
m 0 (h, z, . . . ) 5
x ? f(x, h, z, . . . )
m 1 (h, z, . . . ) 5 ]]]]] dx
m 0 (h, z, . . . )
ith central moment:
m i (h, z, . . . )
q
[x 2 m 1 (h, z, . . . )] ? f(x, h, z, . . . )
5 ]]]]]]]]]] dx
m 0 (h, z, . . . )
p
(i 5 2, 3, . . . )
23
24
Table 2
Equations and references for the EMG
hw
y5]
s
] 2 ]d GJ
2 ]D H1 2 erf F ]
]2 expS]
s
]2 s s
w
2s
]
p
w2
x2z
1 w
x2z
(1)
(2)
(3)
h
y 5 ]]
]
ws2p
Notes
[GsxdE] dt
]
hw2
y 5 ] exp[B 2 2 2AsxdB]
s
(5)
hw
y 5 ] exp[B 2 2 2AsxdB]
s
(8)
hw
y 5 ] exp[B 2 2 2AsxdB]
s
h
y 5 ]]
]
ws2p
[47,48,65,111,187]
t
E 5 exp 2 ]
s
[3335,172]
G I 5 exp
[90,108]
x2t
E Isxd 5 exp 2 ]
s
S D
[50,51]
E IIsxd 5 exp
2t
exp ]
2
dt
[17,81,100]
D S DG
Csxd
1 erf ]
]
2
[81,131]
[GsxdE] dt
[81,131]
hw
y 5 ] exp[B 2 2 2AsxdB]
s
2] A(x)
exp
2z / w
C 2sxd
2]
2
]2 dAsxd
[160]
]
C(x) /2
]
C(x50) /2
exps 2 t 2d dt]
[110]
[G I E IIsxd] dt
[27,61,146]
2`
C(x)
hw ]
p
y 5 ] ] exp[B 2 2 AsxdB] erf ]
s 2
]2
hw ]
p
y 5 ] ] exp[B 2 2 2AsxdB]h1 1 erf[(B 2 A(x))]j
s 2
S D
[7,11]
h
z ]
]
y5]
1 2B 1 erfs A(x) 22Bd
] erf ]
w
ws2
]
[C(x)] 2
[C(x)] 3 [C(x)] 5
hw
p
] exp ]] 1 C(x) 1 ]] 1 ]] 1 K
y 5 ] exph 2 [Asxd] 2 j
s
2
2
3
3.5
h s
[46,145]
H H J
h
y 5 ]]
]
w2p
[17]
[34]
[G I E Isxd] dt
x2z2t
F 2 ]21 s]]
G
w d
s d
t2z
F 2 ]12 s]
G
w d
2
C(x)
z
erf ]
] 1B
w2
h
y5]
s
(18)
dt
exps 2 t 2d dt
FS
(13)
(17)
Gsxd 5 exp
A(x)2B
2`
2`
h
y5]
exp[B 2 2 2AsxdB]
s]
p
(16)
(12)
(15)
Csxd
2]
]2
2 t2
exp ]
2
2C(x)
[23,52,8991,124,125,146,162]
dt
[G I E Isxd] dt
(10)
(14)
2 t2
exp ]
2
h
y 5 ] exp[B 2 2 2AsxdB]
2s
C(x)
2`
[50,51,58,61,75,121,122,129,156,183,185]
(9)
(11)
x2z
A(x) 5 ]
]
w2
w
B5]
]
s2
]
Csxd 52[Asxd 2 B]
exps 2 t 2d dt
1 2 erf
h
y5]
exp[B 2 2 2AsxdB]
s]
p
h
y 5 ]]
]
ws2p
A(x)2B
2`
S D
H F GJ
E S D
h
y 5 ] exp[B 2 2 2AsxdB]
2s
(7)
h
2
y5]
] exp[B 2 2AsxdB]
s2p
(4)
(6)
[7,32,33,42,62,75,108,112,141,142,154,186,188]
[43]
x2t1z
S 2 ]]
D
s
25
Table 4
Equations and references for the Log-normal
y 5 h exp
y 5 h exp
(1)
HF
ln r
2 ]]2 ln
sln s rd
2
sx 2 zdss r 2 1d
]]]] 1 1
wr sr
ln 2
2 ]]
s 2
ln]
w
[8,55,109,145,163]
53
s 2
] 21
sx 2 zd
w
]]]]]
11
s
(s 1 w) ]
w
46 6
[145]
(3)
2ssx 2 zd
H F]]
1 1 GJ J
w
ln 2
2]
ln
s2
SS D D
y 5 h exp
ln
S D
S D
b
1
x2a
y 5 h ]] exps 2 c d exp H 2 ] F lnS]]DG J
x2a
b
2c
(2)
GJ J
[164]
]
hln 2ss 2 2 1d
y 5 ]]]]]]]
exp
lnss 2d
sw lnssd]
p exp ]]
4 ln 2
(4)
H
G
ln 2
2 ]]2 ln
lnssd
2
sx 2 zdss 2 1d
]]]] 1 1
ws
GJ
2
[167]
4. Commercial softwares
Although generic mathematical or graphic softwares could be used in principle for the purpose of
peak fitting, a number of specific programmes have
been described in the literature for the treatment of
chromatograms and spectrograms [4,7,8,16, 24, 25,
31,41,45,51,56 58,61,63,82,84,86,99,101,104,106,
Table 3
Equations and references for the Poisson
y 5 h exp s1 2 ad
(1)
xb
y 5 ]]
exp
b 11
a b!
(2)
x
y5h ]
z
(3)
F]xz 2 lnS]xz D 2 1 GJ
[21,37,74]
(6)
h
y 5 ]]]
]]]
2psa 2 1d
exp[2bsx 2 zd]
[184]
(7)
asx 2 ud
y 5 h ]] exps 2 x 1 ud
a!
[bsx 2 ud] a
y 5 ]]] exp[2bsx 2 ud]
a!
[31]
(8)
b
y 5 h ]sx 2 ud a 21 exp[2b(x 2 u)]
Gsad
[184]
(4)
[a 1 bsx 2 zd] a
y 5 ]]]] exp[2a 2 bsx 2 zd]
a!
[31]
(9)
y 5 h expha[expsixd 2 1]j
[146]
(5)
y5
[31]
(10)
xb
y5]
exp
a b b!
[111]
SD
a 21
S]xz D
aa
]]] exp
sa 2 1d a 21
S 2 ]ax D
a 21
F 2 ]axz 1 a 2 1 G
[178]
[154]
S 2 ]ax D
26
110, 124, 125, 132, 146, 149, 152, 153, 161, 163, 167,
168,173,188].
These programmes were mainly written ad hoc for
personal use. There are however some commercial softwares which can be bought alone or as
modules together with other more general programs.
To our knowledge, the existing softwares are Peaksolve (Galactic) [56], Peakfitter (Microcal)
[125], and Peakfit (SPSS) [167]. These softwares
have been reviewed in the literature (see e.g.
[16,77,82]); therefore we will simply report here
how many and which built-in functions are included in the database of each programme.
Galactic Peaksolve contains only a small number of built-in functions: Gaussian, Log-normal,
Lorentzian, LorentzianGaussian sum, Pearson VII,
Voigt. The absence of the most frequently employed
chromatographic function, the EMG, has to be
underlined.
Microcal Peakfitter divides the built-in functions in chromatographic (Chesler / CramB,
series, EMG, Gaussian, GidEdgeworth / Cramer
dings, Gram / Charlier series), spectroscopic
(Gaussian, Lorentzian, LorentzianGaussian sum,
asymmetric LorentzianGaussian sum, Lorentzian,
Pearson VII, inverse Polynomial, Voigt), generic
peak (Beta, Extreme Value, Gaussian, Logistic, 3parameters Log-normal, Lorentzian, LorentzianGaussian sum, asymmetric LorentzianGaussian
sum, Pearson VII, inverse Polynomial, asymmetric
double Sigmoid, Weibull 3) and other type (exponential, trigonometric, etc.; between them, only the
square Sine can assume a peak-like shape).
SPSS Peakfit lists the highest number of builtin functions, which as for Peakfitter are classified in
different groups: chromatographic (generalized
EMG, EMG1GMG, Extreme Value fronted, Extreme Value tailed, Gaussian, GEMG4, GEMG5,
Giddings, GMG, HVL, Log-normal, NLC),
spectroscopic (Gaussian, constrained Gaussian,
Lorentzian, LorentzianGaussian product, LorentzianGaussian sum, Pearson VII, Voigt), miscellaneous peak (Cumulative, asymmetric Cumulative,
Erf, Intermediate, asymmetric Logistic, Logistic
power, Pulse, Pulse with power term, symmetric
double Sigmoid, asymmetric double Sigmoid),
statistical (Beta, Error, 4-parameters Extreme
Value, Extreme Value fronted, Extreme Value tailed,
5. Conclusions
In this paper, we collected and tabulated 86
functions proposed for the representation of chromatographic peaks. The most used name, the most
convenient equation, the applications, the mathematical properties (in relation to the possible applications) and a list of references are reported for each
function (Table 1). The built-in functions employed
in some commercial peak-fitting software packages
have been included, too.
An important objective of this work has been the
individuation and elimination of a number of ambiguities, which sometimes appear to have propagated, in the denomination of the reported functions. Quite often the same name has been assigned
to different functions, or conversely a single function
has been designated with different names. We underlined these cases, which especially (but not only)
27
Table 5
series
Equations and references for the Edgeworth / Cramer
y 5 h exp
F S D G H1 1 O
1 x2z
2 ] ]]
2
w
n
i 51
s 2 1d i
i
j 51
floors(i 12 ) / 2d
k 50
O Q s 2 td
O hs 2 1d O fs 2 1d c
y 5 G(t) 1 O hs 2 1d O f c
G
y 5 G(t) 1
(2)
y 5 G(t) 1 1
(3)
i 51
n
i 51
j 51
i 51
jj
[3638,111,155]
[134]
[134]
G std
Hi (t)5(21)i ]] (Hermite pol.)
G(t)
(i )
si 12jd
j 51
GJJJ
Notes
(1)
x 2 z i 1222k
s 2 1d k ]]
w
]]]]]
2 k k!si 1 2 2 2kd!
std g
i,i 12j
x2z
F 2 ]12 S]]
DG
w
2
G(t) 5 h exp
h
or ]]
] exp
w2p
regard the Gamma, Giddings, Log-normal and Poisson functions, and proposed unambiguous names.
Some of the most important chromatographic
functions, i.e. the Exponentially Modified Gaussian
(EMG), the Poisson, the Log-normal, the
series and the Gram / Charlier
Edgeworth / Cramer
series, have been reviewed and commented in more
detail. Tables 26 list all the equations which have
been used to represent these functions. Several of the
equations employed in the literature for the EMG
x2z
F 2 ]12 S]]
DG
w
2
Table 6
Equations and references for the Gram / Charlier series
y 5 h exp
F S DGO
1 x2z
2 ] ]]
2
w
n
i 50
s 2 1d i c i
floorsi / 2d
j 50
y 5 G(t)
(2)
y 5 G(t) 1 1
(3)
y5
GJ
Notes
H (t)
G
O Fs 2 1d c ]
i!
(1)
x 2 z i 22j
s 2 1d j ]]
w
]]]]]
2 j j!si 2 2jd!
i 50
H O F
n
i 53
Hi (t)
s 2 1d i c i ]
i!
c G (t)
J
O H]]
i!
GJ
[36,73,123,134]
c i : see [134]
[72,125,130,178]
G std
Hi (t)5(21)i ]] (Hermite pol.)
G(t)
[119,134]
G(t) 5 h exp
(i )
(i )
i 50
x2z
F 2 ]12 S]]
DG
w
2
h
or ]]
] exp
w2p
x2z
F 2 ]12 S]]
DG
w
2
28
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