hansen solubility parameters in chromatographic sciences 04... · 2017. 3. 29. · b.l.karger,...
TRANSCRIPT
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HANSEN SOLUBILITY PARAMETERS IN CHROMATOGRAPHIC SCIENCES
ADAM VOELKEL, K. ADAMSKA
POZNAŃ UNIVERSITY OF TECHNOLOGY, POLAND
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• Energy of vaporization
• Cohesive energy density
SOLUBILITY PARAMETER THEORY
dVV
UUE
V
VparVT
g
l
V
Ec
V
RTH
V
Ec wcoh
Solubility parameter units : cal/cm3)1/2, (J/m3)1/2, (MPa)1/2
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HANSEN SOLUBILITY PARAMETERS (HSP)
hpd EEEE
V
E
V
E
V
E
V
E hpd
2222
hpdT
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R.Tijssen H.A.H.Billet, P.J.Schoenmakers, Use of solubility parameters for predicting selectivity and retention
in Chromatography, J.Chromatogr., 122 (1976) 185-203
𝛿𝑇2 = 𝛿𝑑
2 + 𝛿𝑜2 + 𝛿𝑎𝛿𝑏
𝑙𝑛 𝛾𝑖ℎ =
𝑉𝑖
𝑅𝑇𝛿𝑑
𝑖 − 𝛿𝑑𝑗 2
+ 𝛿𝑜𝑖 − 𝛿𝑜
𝑗 2+ 2 𝛿𝑎
𝑖 − 𝛿𝑎𝑗
𝛿𝑏𝑖 − 𝛿𝑏
𝑗
ln𝐾𝑖 =𝑉𝑖
𝑅𝑇𝛿𝑇
𝑚2 − 𝛿𝑇𝑆2 + 2𝛿𝑑
𝑖 𝛿𝑑𝑆 − 𝛿𝑑
𝑚 + 2𝛿𝑜𝑖 𝛿𝑜
𝑆 − 𝛿𝑜𝑚 + 2𝛿𝑎
𝑖 𝛿𝑏𝑆 − 𝛿𝑏
𝑚 + 2𝛿𝑏𝑖 𝛿𝑎
𝑆 − 𝛿𝑎𝑚
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B.L.Karger, L.Snyder, C. Eon, Expanded Solubility Parameter Treatment for Classification and
Use of Chromatographic Solvents and Adsorbents, Analytical Chemistry, 50 (1978) 2126-2136
∆𝐸𝑙𝑠𝑐 = −𝑛 ∆𝐸𝐴
𝑗 𝑎𝑑 − ∆𝐸𝑠
𝑖 𝑗 + ∆𝐸𝐴
𝑖 𝑗 + ∆𝐸𝐴
𝑖 𝑎𝑑
j = solvent; ad – adsorbent; i = solute
∆𝐸𝑠 𝑖 𝑗 = 𝑉𝑖 𝛿𝑗
2− 2𝛿𝑑
𝑖 𝛿𝑑𝑗− 2𝛿𝑜
𝑖𝛿𝑜𝑗− 2𝛿𝑖𝑛
𝑖 𝛿𝑖𝑛𝑗
− 2𝛿𝑎𝑖 𝛿𝑏
𝑗− 2𝛿𝑎
𝑗𝛿𝑏
𝑖
∆𝐸𝐴 𝑖 𝑎𝑑 = 𝑉𝑖 𝛿𝑑
𝑖 𝛿𝑑𝑎𝑑 + 𝛿𝑜
𝑖𝛿𝑜𝑎𝑑 + 𝛿𝑖𝑛
𝑎𝑑𝛿𝑑𝑖 + 𝛿𝑖𝑛
𝑖 𝛿𝑑𝑎𝑑 + 𝛿𝑎
𝑖 𝛿𝑏𝑎𝑑 + 𝛿𝑎
𝑎𝑑𝛿𝑏𝑖
∆𝐸𝑙𝑠𝑐= ∆𝐸𝐴
𝑖 𝑎𝑑 −𝐴𝑖𝐴𝑗
∆𝐸𝐴 𝑗 𝑎𝑑
Ai, Aj – molecular area of “i” and “j”; 𝛿 – total solubility parameter; 𝛿𝑑 - dispersion solubility
parameter; 𝛿𝑜 - orientation solubility parameter; 𝛿𝑖𝑛 - induction solubility parameter;
𝛿𝑎 - proton donor solubility parameter; 𝛿𝑏 - proton akceptor solubility parameter
Liquid solid chromatography
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B.L.Karger, L.Snyder, C. Eon, Expanded Solubility Parameter Treatment for Classification and
Use of Chromatographic Solvents and Adsorbents, Analytical Chemistry, 50 (1978) 2126-2136
𝑖 𝑗 ↔ 𝑖 𝑘
Liquid liquid chromatography
j = solvent; k – liquid stationary phase; i = solute
∆𝐸𝑀 = 𝑉𝑖 𝛿𝑖2+ 𝛿𝑗
2− 2𝛿𝑑
𝑖 𝛿𝑑𝑗− 2𝛿𝑖𝑛
𝑖 𝛿𝑑𝑗− 2𝛿𝑖𝑛
𝑗𝛿𝑑
𝑖 − 2𝛿𝑎𝑖 𝛿𝑏
𝑗− 2𝛿𝑎
𝑗𝛿𝑏
𝑖
ibj
aj
bia
id
jin
jd
iin
jo
io
jd
id
jiS VE 2222222
jMkMllc EEE jSkS
llc EEE
∆𝐸𝑙𝑙𝑐
= 𝑉𝑖 𝛿𝑘2− 𝛿𝑗
2− 2𝛿𝑑
𝑖 𝛿𝑑𝑘 − 𝛿𝑑
𝑗− 2𝛿𝑖𝑛
𝑖 𝛿𝑑𝑘 − 𝛿𝑑
𝑗− 2𝛿𝑑
𝑖 𝛿𝑖𝑛𝑘 − 𝛿𝑖𝑛
𝑗− 2𝛿𝑜
𝑖 𝛿𝑜𝑘 − 𝛿𝑜
𝑗
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B.L.Karger, L.Snyder, C. Eon, Expanded Solubility Parameter Treatment for Classification and
Use of Chromatographic Solvents and Adsorbents, Analytical Chemistry, 50 (1978) 2126-2136
Retention in gas-liquid chromatography
𝛿𝐼 𝑖 𝑗 = 𝑅𝐼 𝑖 𝑗 − 𝑅𝐼 𝑎𝑙 𝑗
𝛿𝐼 𝑖 𝑗 =200 𝑉𝑖
∆𝐸𝑆 𝐶𝐻2 𝑗𝛿𝑎𝑙 − 𝛿𝑑
𝑖 𝛿𝑑𝑗+ 𝛿𝑖𝑛
𝑗− 𝛿𝑜
𝑖𝛿𝑜𝑗− 𝛿𝑖𝑛
𝑖 𝛿𝑑𝑗− 𝛿𝑎
𝑖 𝛿𝑏𝑗− 𝛿𝑏
𝑖𝛿𝑎𝑗
𝛿𝐼 𝑖 𝑗 retention index difference between a solute „i” and hypothetical n-alkane „al” ofthe same molar volume as „i” on stationary phase „j”
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•Flory–Huggins interaction parameter
SOLUBILITY PARAMETER – IGC
o
oo
o
go V
V
ρ
ρVB
TR
p
MVp
Rχ
2
1
2
1111
1
11
12 1ln15.273
ln
1 and 2 denotes the solute and examined material, M1-the molecular weight
of the solute, p10-the saturated vapor pressure of the solute, B11-the second
virial coefficient of the solute,V10 -the molar volume, i-the density,
R -the gas constant.
115.273ln 111111
212
o
o
o
g
oVB
TR
p
VVp
Rχ
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GUILLET - DI PAOLA BARANYI APPROACH
s
RT
V
2
211
i
si
i
ii
VRTRTVRT 1
2
21
2
1
)12(2
1 2
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• Combination of the experimental data of Flory-Hugginsinteraction parameter with components of solubility
parameter for test solute and examined material
HSP THROUGH IGC PROCEDURES
2,2,12,2,12,2,1112 25,025,0 hhppddo
RT
V
where α, V , R, T are a corrective coefficient, molar volume of the test solute, gas constant and temperature
of measurement, respectively.
K. Adamska, R. Bellinghausen, A. Voelkel, New procedure of the determination
of Hansen Solubility Parameters by means of inverse gas chromatography,
J. Chromatogr. A, 1195 (2008) 146-149.
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BASIC RELATIONS
LSLSGLGLLLN AKAKKVV
Tm
FjtV
w
Rg
15.273
2
3'
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• Model of adsorption described by Snyder and Karger
SOLUBILITY PARAMETER FOR SOLIDS
constRTEV Ag ln
jhihjpipjdidiA VE
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HSP FOR SOLIDS
N
n
N
n
NhNNpNNdN
nhnnpnndn
hpd
N
n
...
...
...
...
*
VVV
.........
VVV
.........
VVV
E
...
E
...
E
111111111
XY
•Y - the column vector containing the N values of experimental measurements of the energy of
adsorption ( -EN) of N solutes,
•X - the experimental matrix, formed of elements (Xnk) , where , Vn is the molar volume of the nth
solute and is one of the Hansen Solubility Parameters of type k (k = d, p, or h) of the
respective test solute,
•Β - the vector which contains the real values of HSPs of the adsorbent,•ε – the vector which corresponds to the experimental errors, εn.
nk
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K. Bielicka-Daszkiewicza, A. Voelkel, M. Pietrzyńska, K. Heberger, J. Chromatogr. A, 1217 (2010) 5564–5570
Role of Hansen solubility parameters in solid phase extraction
HSPs and total solubility parameter for sorbents, eluents and analytes
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K. Bielicka-Daszkiewicza, A. Voelkel, M. Pietrzyńska, K. Heberger, J. Chromatogr. A, 1217 (2010) 5564–5570
:
left – indicated position of solvents right - indicated position of sorbents
Score plots for sorbent-analyte, solvent-analyte, sorbent-solvent systems
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I tutaj tabelki z posteru
Squares of differences fo sorbent-solvent (eluent) pairs
Squares of differences fo sorbent-analyte pairs
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Taking into account that the use of ethanol allowed to achieve better recovery, it can be
concluded that:
i) the sorbent for which the lowest (δP –δA)2 value is found should be selected as a material
of filling the needle device;
ii) the value of (δP-δS)2 does not have to be as small as possible,
iii) the interactions between the analyte and the solvent are more important for the
extraction process than the interactions between the polymer and solvent.
Therefore, for the selection of a suitable extraction system should start from finding lowest
value for (δP-δA)2.
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THANK YOU FOR YOUR ATTENTION
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