Download - HCOOH NMR presentation
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NMR titrationHCOOH; CH3COOH; NaNO2
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HCOOH1) 1.0 μL H2SO4 50 μL H2
18O
18
18
18
18
2) 40.5 μL DMF570 μL D2O
18
18
18
18
40 μL 1.5M
3) 6 μL 50% NaOH per aliquot during titration
unlabeled Monolabeled dilabeled
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HCOOH (fully protonated) and DMF
NB1p20formic1_C_part-1.jdf
165.9 165.8 165.7 165.6 165.5 165.4 165.3 165.2 165.1 165.0 164.9 164.8 164.7 164.6Chemical Shift (ppm)
unlabeled
dilabeled
monolabeled
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B1P2O-a #284-310 RT: 1.43-1.56 AV: 27 SB: 13 1.18-1.24 NL: 3.21E6T: - c Full ms [ 30.00-80.00]
38 40 42 44 46 48 50 52 54 56 58m/z
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Rel
ativ
e A
bund
ance
47.12
45.11
49.12
46.28 48.2044.34 58.3657.1950.1042.02 43.2240.17
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Formic Acid.esp
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
Standardization: credit to Katie
All acid (0% reacted)
Predicted 50%-reacted point
All formate (100% reacted with NaOH)
DMF
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Many thanks to Katie for standardization(δun
0-δun)(δmono-δmono-)= (δun-δun-)(δmono0-δmono)
calibration
0 1 2 3 4 5 6 7 80
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f(x) = 1.0134289299868 x − 0.000509406394531009R² = 0.999999912992084
un/mono16O16O/16O18O
(δun-δun-)(δmono0-δmono)
(δun
0-δu
n)(δ
mon
o-δm
ono-
)
• δ0:shift of acid prior to adding base
• δ-:shift of anion when acid-base rxn is complete
• Other variables dependent on extent of ionization
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Mono/di unnecessary? For mono/di: (δmono
0-δmono)(δdi-δdi-)= (δmono-δmono-)(δdi0-δdi)
un/mono VS mono/di
0 1 2 3 4 5 6 7 80
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f(x) = 1.0134289299868 x − 0.000509406394531009R² = 0.999999912992084
un/mono16O16O/16O18O
(δun-δun-)(δmono0-δmono)
(δun
0-δu
n)(δ
mon
o-δm
ono-
)
0 1 2 3 4 5 6 7 80
1
2
3
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f(x) = 1.0136595412 x − 0.0014119207R² = 0.999999811668334
mono/di16O18O/18O18O
(δm
ono0
-δm
ono)
(δdi
-δdi
-)
(δmono-δmono-)(δdi0-δdi)
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(δun0-δun)(δdi-δdi-) =(δun-δun-)(δdi
0-δdi)
16O16O/18O18O (un/di)
0 1 2 3 4 5 6 7 80
1
2
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8
f(x) = 1.0272702612 x − 0.0019261323R² = 0.999999743202866
un/di16O16O/18O18O
(δun-δun-)(δdi0-δdi)
(δun
0-δu
n)(δ
di-δ
di-)
Ka ratio:Un/mono/di = 1.0273/1.0137/1
18
18 18
18
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Acetic acid (fully protonated)
Inez_NB1p11_Sample2_13C-4.jdf
176.55 176.50 176.45 176.40 176.35 176.30 176.25 176.20 176.15 176.10Chemical Shift (ppm)
Significant increase in height after more unlabeled acetic acid is added
18
18
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CH3COOH and DMF credit to KatieAcetic Acid.esp
16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
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Calibration
Many thanks to Katie for standardization
0 1 2 3 4 5 60
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2
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f(x) = 1.01250562256214 x + 0.000137612538945398R² = 0.999999683533146
UN/MONO
0 1 2 3 4 5 601234567
f(x) = 1.01167825599676 x + 0.00568749995565909R² = 0.999993388828339
MONO/DI
0 1 2 3 4 5 601234567
f(x) = 1.02441687216787 x + 0.00538982102030294R² = 0.999993059171215
UN/DI
Kaun:Kamono:Kadi:
CH3COOH: 1.0244:1.0117:1
HCOOH: 1.0273:1.0137:1
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Blp22-a #356-383 RT: 2.01-2.16 AV: 28 SB: 41 1.48-1.71 NL: 3.75E5T: - c Full ms [ 30.00-80.00]
30 35 40 45 50 55 60 65 70 75 80m/z
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Rel
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e A
bund
ance
62.18
46.16
47.2036.68
Attempted HNO2 synthesis
[M1-H]-
[M2-H]-
BlP22ESI Negative Ion Mode
HNO2
HNO3
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Na15NO2 SPECTRA
181818
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18
1818