© 2021 ACS Division of Organic Chemistry

Author: Prof. Hans Reich Updated 4/11/2022

Equilibrium pKa Table (DMSO Solvent and Reference)

Ketones Ketones Ketones Esters

O O
O O
58 27.11 X
X Ph Ph 18.7 EtO
O O X= H 29.544
X= H 26.552 27.758 +
Ph 19.858 Ph 19.4 58 NMe3 20.044
+
OMe 24.627 Py 14.144
SPh 18.7 Ph O Ph 22.718
COCH3 13.3 O 26.358 CN 13.118
S(O)Ph 15.1 18.858 Ph (MeO) SPh 21.452
Ph
SO2Ph 12.558 Ph
O SO2CF3 6.461
+
NMe3 16.344 NO2 9.161
+
Ph 28.258
Py 11.844 O n O
3 28.2
O Ph t-BuO 30.3
n 4 24.9 β -Diketones
5 25.8 O
Ar O O
6 26.758 Ph 23.618
Ar = Ph 24.71 7 27.7 t-BuO
2-Py 23.6 S
8 27.4
4-Py 21.8 X Ph 16.951
2-Furyl 23.9 O n X= H 13.342 PhO
4 26.2 Me 15.142 O
2-Thienyl 24.0
n 5 25.851 Et 15.343 Ph 18.751
PhO
O 6 26.451 Ac 8.643 O
7 27.8 Ph
X
8 27.4
O O 16.951
Ph 42
PhS
10 26.7 13.4
X= H 24.752 Ph Ph O
Me 24.458 12 26.9
O O N=CHPh 19.538
Ph 17.758 EtO
O 14.258
COMe 14.258 Me Ph O O
COPh 13.442 24.859 14.258
X EtO
C≡N 10.26
O OX= O
F 21.752
H 11.242 S
OPh 21.134 O Me 11.343 MeO 20.9
OMe 22.934
25.8 Ac 9.843 S
NPh2 20.3
NMe2 23.657 O O O O
+
NMe3 14.66 51 10.359
+ O 16.9 11.559
Py 10.744 O
NO2 7.76 O O
O
SPh 17.135
SO2Ph 11.46 Malonate Esters
24.7 18.242
SePh 18.65 O O
O
EtO OEt
O 29.0 O O
14.2 52 X
X EtO X= H 16.442
+
X= H 24.71 NMe3 11.844
O 28.1 Lactones +
Py 5.644
p-Me 25.2
p-Ph 24.5 O O O
p-OMe 25.750 25.5 O 13.551
m-OMe 24.550 O MeO OMe
p-NMe2 27.550 O X
m-NMe2 25.350 S 10.751
p-F 24.550 O 32.4 X= H 15.943
m-F 23.550 Me 18.043
p-Cl 23.850 O Et 18.543
m-Cl 23.250 CO2Me 10.843
O O O 25.259 CF3 10.8
p-Br 23.850
p-SPh 23.850 S O
10.153 X
p-S(O)Ph 23.2 O O
p-SO2Ph 22.150 O O 23.359
m-SO2Ph 23.050 O O O
p-C≡N 22.050 O
p-CF3 22.750
24.559 X= H 7.343
m-CF3 22.850 O
Me 7.443
Et 7.643
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)
Amides (C-H) Amides (NH) Amides (NH) Nitriles
N
O O H C
X
H (35) N O
Et2N R NH2 20.751 X= H 31.31
O R= H 23.5 13 Me 32.55
+ Me 25.513 Ph 21.99
NMe3 24.9 44
Et2N CH2OPh 23.027 C6F5 15.837
CH2OMe 23.927 N H 26.651 2-Furyl 21.4
O CH2SPh 23.027 1-Naphthyl 20.960
Ph 26.618 CH2F 22.327 O 2-Naphthyl 20.760
Me2N CH2NH2 24.7 9-Anthryl 19.860
O
CH2NMe3+ 15.327 COPh 10.26
SPh 25.918 O
Me2N Ph 23.341 N H 25.4
O 3-Py 22.027 C-N 17.218
+ 4-Py 21.627
NMe3 24.918 O
Me2N 2-Fu 22.5 CO2Et 13.118
O O CF3 17.252 C≡N 11.11
N H X = O 17.0
18.251 OEt 24.251 OPh 28.15
X = S 13.3 +
Me2N NH2 26.9 NMe3 20.66
X +
O Py 16.544
O SPh 20.85
Ph X N H
CN R N SMe 24.336
N 17.218
H SO2Ph 12.06
X = O 14.8
S R = Me 21.541 X = S 11.9
25.751 X O
Ph 18.841 X N
Me2N Me CH2F 18.2 C
CH2OMe 19.4 N H X= H 21.99,60
S
21.3 51 CH2SPh 19.0 X = H 14.1 p-Me 22.960
Ph N
CF3 12.6
Me2N H O X = F 12.7 Me3 24.6
p-Ph 20.860
N≡C-NH2 17.057 p-Bz 16.060
18.551 O Carbamates (NH) p-NMe2 24.660
O
N =S 51 Me O p-OMe 23.860
10.0 25.957
Me N Et m-OMe 21.660
24.251 p-F 22.237,60
H O NH2
S m-F 20.037,60
O 13.551 O
18.541 o-F 20.437
N Me NH2 p-Cl 20.560
H 20.851
Ac
O N m-Cl 19.560
X
X = O 23.3 m-Br 19.460
41
Ph NH2 = S 16.9
X p-CN 16.060
m-CN 18.760
Nitro
O p-NO2 12.360
O2N-CH2-X m-NO2 18.160
3,5-(CF3)2Ph NH2 16.941 X= H 17.21 m-CF3 19.260
Me 16.71 p-SPh 19.660
X Et 17.0 m-SPh 20.460
Ph 12.29 p-SO2Ph 15.860
X = O 24.251
N H SPh 11.810 m-SO2Ph 18.560
X = S 13.3
SO2Ph 7.16 (NC)2CHCH3 12.413
COPh 7.76 N≡CCHPh2 17.59,60
O 18.551 CH=CH2 11.3 N≡CCH(C6F5)2 8.037
N =S 10.051 N≡C-Fl 8.31
H PhCH(Me)CN 23.060
O2N 16.92
O Malononitriles
N N
N H 14.7 NO2 n= 3 26.912 C C
4 17.812
O n 5 16.012 R
6 17.912
O 7 15.812 R= H 11.11
Me Me 12.413
N 4.2
N H 15.048 Ph
Acetylenes pClC6H4 3.1
O Ph-C≡C-H 28.81,23 pMeOC6H4 5.6
tBu 13.2
NH2 13.734
NMe2
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)
Hydrocarbons Hydrocarbons Fluorenes Oxazole
X O
CH4 (~56)52 Ph Ph = Fl-X H 24.452
25.8
N
(~59)19 Ph Ph
Imidazolium
30.19 Me
X= H 22.61 N
X CH3 Me 22.31 18.652
H
Et 22.321 N+
X= H (~43)11 30.09 Pr 22.2
C≡N 30.811 i
Pr 23.221 Me
O
NO2 20.411 t
Bu 24.421 iPr
+
NMe3 31.944 18.019 i-Bu 21.6 N
+
Py 20.544 CH2tBu 20.3 H 24.49
COPh 26.911 Ph 17.91 N+
SO2Ph 29.811 26.122 o-Tol 18.8
SO2CF3 24.011 p-Tol 18.3 iPr
Thiazole
C6F5 14.8
X CH2OH 23.2 S
20.117 29.452
SiMe3 21.526 H
SiPh3 18.626 N
C(O)Ph 10.0
10.31 S
21.822 CO2Me
16.530
C(O)SEt 8.8 H
C(O)NH2 14.8 Me N+
X= H 31.1
OMe 30.6 22 CN 8.31 Me
22.5
OPh 30.2 NC 12.352
S
SHex 29.9 NO2 7.1 27.052
NH2 22.134 H
SPh 28.6 N
CH3 32.4 NMe2 22.534
17.317
CN 19.7 +NMe3 17.833 S
NO2 12.7
+
Py 11.844 CH3 30.352
+
Ph PPh3 6.633 N
Me
OMe 22.15
Heteroaromatics S
OiPr 21.45 13.940
OtBu 21.35 CH3
OPh 19.95 Me N+
28.2 SMe 18.07 Me
Ph
X N SiPr 16.9
StBu 15.9
Allyl
X= H 31.1
CH3 31.8 25.2 SPh 15.55 CH2=CH-CH3 (44)52
Cl 28.2 Ph S(O)Ph 15.1
+N
S(O)Bn 15.7 (CH2=CH)2CH2 35.19
Br 28.4
CN 20.0 O S(O2)Me 12.8 Ph Ph
NO2 13.2 S(O2)Et 12.3
Ph Ph 25.852
30.1 S(O2)tBu 12.3
Ph2CH2 32.33 N Ph S(O2)Ph 11.5
Ph N Ph
(CH2=CH)2CH2 35.19 F 22.3
(C6F5)2CH2 22.037 N Cl 18.9 26.5
26.7 Ph Ph
(p-O2N-C6H4)2CH2 15.254 Ph +
Ph3CH 30.61 Ph3P-CH2-CH=CH2 18.529
+
(p-Cl-C6H4)3CH 27.0 N Ph3P-CH2-CH=CHPh 15.629
(p-O2N-C6H4)3CH 12.754 (35)52
PhS SPh 26.3

Ph PhSe SePh
26.3
30.2
O PhSO2-CH2CH=CH2 22.552
Ph O2N-CH2CH=CH2 11.3
30.0
S O O
S Ph 20.251
Ph
Propargyl
PhSO2-CH2C≡CH 22.1
PhSO2-CH2C≡CPh 17.8
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)

Sulfides Sulfimides Sulfones Sulfones

N-Ts O O
MeS-CH3 (45)52 O O
S 27.6 S X S
PhS-CH2-X Ph Me Ph CH2Ph
52 1
X
X=H (42) N-SO2Ph X=H 29.0
Ph 30.810 30.7 Me 31.05 X = Me 25.455
S t
Bu 24.921
C≡N 20.85 Ph t-Bu 31.25
COMe 18.710 Ph 23.41 NMePh 24.153
COPh 17.135 α-Naphth 22.5 CH2Ph 23.952
NO2 11.810 β-Naphth 22.31 CF3 14.652
+ Sulfonium Salts
NMe3 28.044 2-Py 20.5 CF3-SO2-CH3 18.82
+
Py 17.744 + 3-Py 21.6
Me3S=O 18.2 CF3-SO2-Et 20.4
SPh 30.83 4-Py 18.6 CF3-SO2-i-Pr 21.82
SO2Ph 20.55 Me CH=CH2 22.5 O
+
SO2CF3 11.010 Ph S 16.3 CH=CHPh 20.251 CF3-S 26.62
POPh2 24.9 Ph C≡CH 22.1
C≡CPh 17.8 O
MeS-CH2-SO2Ph 23.45 Me
MeS-Fl 18.07 + COMe 12.55 (CF3-SO2)2CH2 2.152
Me S 17.832 Ph-SO2-CHPh2 22.39
PhS-Fl 15.55 COPh 11.45
Ph (PhSO2)2CHMe 14.310
MeS-CH2-CN 24.321 C≡N 12.05
t-BuS-CH2-CN 22.921
+ OPh 27.95 PhSO2CH(SiMe3)2 20.426
Fl-SMe2 6.532
PhSCHPh2 26.710 OMe 30.75
+ PhSO2-CH2CH=CH2 22.552
(PhS)2CHPh 23.010 Sulfoximides (C-H) NMe3 19.45
NO2 7.15 O O
PhS SPh 26.3 NMe S Ph 20.251
SMe 23.45
Ph-S-Me 33.0 15 Ph
S SPh 20.55
O SO2Ph 12.26 PhSO2-CH2C≡CH 22.1
X
NTs PPh2 20.23 PhSO2-CH2C≡CPh 17.8
S
Ph-S-CH2-X SiMe3 26.126
X= H (39)23 PhSO2 CH3 29.8
O X=H SiPh3 21.326
Ph 30.710 24.515
F 28.552
PhPh 29.023 Cl 20.7
Cl 23.852 CF3SO2 CH3 24.1
CO2Me 20.823
NTs
C≡N 19.123 Ph-SO2-i-Pr 32.1
(PhS)3CH 22.810 Ph-S-CH(SiMe3)2 19.126 O O
O
(PrS)3CH 31.352 O S
Ph-S 31.8 11.851
NSO2Ph
S O
Ph-S 28.5 Ph
30.510 O O
S S O 52
H S 31.1 (MeSO2)2CH2 15.021
NSO2Ph Me Me
Selenides Ph-S 28.7 O O O O
O O S 32.8 9 S
Et Et 10.153
SePh 18.65 N Me2 +
Ph
Ph-S-Me 14.415 O
PhSeCHPh2 27.5 O
(PhSe)2CH2 31.3
PhSeCH2Ph 31.0 Sulfonates
(PhSe)2CHPh 16.252 O
PhSe SePh Me-S-OPh 25.2
26.3 O
O
Sulfoxides PhCH2-S-OPh 19.953
O O
S X O
Ph PhCH2-S-SPh 19.1
X=H 33.15 O
Ph 27.2
O
SOPh 18.2
O PhCH2-S-F 16.9
S X O
Me Sulfonamides (C-H)
X=H 35.11
SMe 29.0 O O
Ph 29.01 Ph S
O N CH2Ph 24.153
S
Ph CHPh2 24.6
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)

Halides Ethers Phosphines Phosphonates

Ph-SO2-CH2-X 3 O
PhO-CH3 (49)52 Ph2P-CH2-PPh2 29.9
X=H 29.01
28.552 Ph2P-CH2-SO2Ph 20.23 EtO P X
F MeO-CH2COPh 22.95 EtO
Cl 23.8 X = Ph 27.6
O PhO-CH2COPh 21.15 Phosphonium (As) Salts C≡N 16.4
Ph-S-CH2-Cl 20.7 MeO-CH2SO2Ph 30.75 + CO2Et 18.6
NTs Ph3P-CH2-X Cl 26.2
PhO-CH2SO2Ph 27.95
O X=H 22.433 SiMe3 28.752
PhO-CH2C≡N 28.15 Ph 17.433
Ph-S-CHCl2 16.9 O
NTs X p-C6H4-CN 13.029
= Fl-X MeO P X
O p-C6H4-NO2 11.029
MeO
p-C6H4-OEt 18.829 X = Cl 26.2
(MeO)2P-CH2Cl 26.2
SPh 14.933
O CO2Et 8.533 O
F COMe 7.133 MeO P R
Ph 20.252 X=H 22.621 CHO 6.133 MeO N
Ph 17.952 CN 6.933 H
F
MeO 22.15 COPh 6.033 R =H 23.2
iPrO 21.45 +
Ph3P-CHMeCO2Et 9.333 Me 24.9
tBuO 21.35 + Ph 18.3
Silanes (C-H) PhO 19.95 Ph3P-Pr-i 21.2
+
O O X Ph3P-CH2-C6H4CN 13.029 Phosphine Oxides
+
S X Ph3As-CH2-C6H4CN 17.029 O
Ph +
X=H 29.0 1
Ph3P-CH2-CH=CH2 18.5 29 Ph P X
SiMe3 26.126 + Ph
SiPh3 21.326 Ph3PCH2-CH=CHPh 15.629 X = SPh 24.9
+
O Ph3P-Fl 6.633 S
C≡N 16.9
X= H 31.1
EtO P SiMe3 28.752 16.3
EtO OMe 30.6 Ph P C≡N
OPh 30.2 Ph
PhSO2CH(SiMe3)2 20.426 S S
NTs Ph P P Ph 19.3
Ph-S-CH(SiMe3)2 19.126 Ph Ph
O
X
= Fl-X

X= H 22.61
Me 22.31
SiMe3 21.526
SiEt3 21.426
SiPh3 18.626

Germanes (Ge-H)
Ph3Ge-H 23.163
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)

Amines (CH) Ammonium Salts (NH) Ammonium Salts (CH) Pyrrole, Indole (N-H)
O +
NH4+ 10.552 Me3N-CH2-X N-H 23.019
NPh2 20.352 BuNH3+ 11.164
Ph H
PhNH3+ 3.864 X=H (42)33,44
X SO2Ph 19.45 N
= Fl-X 21.019
C≡N 20.65
R NMe2H+ COMe 16.333
H
COPh 14.65
R= H 2.4 CO2Et 20.033 N 19.919
X= H 22.6 52 OMe 3.6 CONEt2 24.918
NMe2 22.536 Me 3.0 CONEt2 15.327
NEt2 21.436 + Ph 31.933
Et3N H 9.047,64
NiPr2 22.536 + SPh 28.033 Azoles (NH)
+
BnNH3 10.264 1-Py-CH2-X
+
N 18.236 BnMe2N H 7.647 X = C≡N 16.544 N-H 18.652
+ COMe 11.844 N
Bn3N H 3.746 COPh 10.744
H CO2Et 14.144 N-H 19.852
Amines (NH) +N 11.164 CONEt2 24.918
H N
NH3 (41)19 Ph 20.544
N
SPh 17.744 N-H 14.852
N-H (44)19 +
+N 45 N
9.8 Me3N-Fl 17.8 33

H Py+-Fl 11.844 N-H 13.952

X NH2 N N
N 8.9 45,64

11,54
N N
X= H 30.6 +
H N-H 8.252
m-CH3 31.011,54 N N
p-Ac 25.354 H H
+N 10.964
p-Bz 24.454 H N
p-F 30.754 Isocyanide 16.452
o-F 28.754 H 64
o-Cl 27.654
O +N 9.2 PhCH2N=C 27.452 N
H
28.554 NC
m-Cl 12.352 NH2 H
p-Cl 29.454 H
Me2N + NMe2 45 N 15.3
m-Br 28.454 7.5 N
p-Br 29.154 Bu
m-OMe 30.554 N N
p-C≡N 25.311
m-C≡N 27.511 Imines (CH) Oximes (OH)
+
p-PhCO 24.411 N H 3.452 NOH
NCH2Ph
p-PhS 28.254 20.231
p-PhSO2 24.911,54 + 14.4 Ph H
p-MeSO2 25.654 N H 4.1 p-NO2-C6H4 17.031
p-CF3SO2 21.854 NOH
p-CF3 27.054 Ph N Ph
m-CF3 28.254 Imides (NH) 28.531
O Me H
p-NO2 20.911,54 26.5 NOH
H Ph Ph 25.231
N
N N H Ph N Ph Me Me
N
NH2 27.754 R R = H 13.148 24.352 NOH 20.131
O R = Ph 9.948 Ph
N O Ph Ph
O NOH
NH2 28.5 H Ph N
N OEt 22.1 14.931
11.048 Ph
N Ph EtO
N
N NH2 54 H
26.5 O
O Imines (NH)
N≡C-NH2 17.019 O NH
16
31.041
Ph2NH 25.0 N H Ph Ph
N
R R = H 15.148
48
O R = Me 15.0
O

N H 14.7

O
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (DMSO Solvent and Reference)

Alcohols (OH) Thiols (SH) Hydrazide (NH) Hydrazone (NH)

O N-NHPh
HOH 31.424 X SH
MeOH 29.024 21.852 21.6
Me NHNH2 Ph Me
EtOH 29.824 20 O
X= H 10.3
i-PrOH 30.324 18.952 N-NHPh
OMe 11.220
t-BuOH 32.224 Ph NHNH2 21.1
Br 9.020 Ph H
CF3CH2OH 23.552
NO2 5.520 PhSO2-NHNH2 17.1 52
N-NHPh
(CF3)2CHOH 17.9
(CF3)3COH 10.752 t-BuSH 17.9 PhSO2-NHNMe2 15.852
14.9
n-BuSH 17.0 Me(C=O)-NHNH2 21.827
Phenols (OH) MeO2CCH2-SH 12.9
PhCH2-SH 15.3 Ac-NHNH-Ac 16.756
X OH PhC(O)-SH 5.262 Ph(C=O)-NHNMe2 19.7 Hydrazine (NH)
Ph-SeH 7.162 27
Ph(C=O)-NHNH2 18.9
X= H 18.025 Ph-NHNH-Ph 26.256
Me 18.925 Ph(C=O)-NHNMe2 19.727
Ph-NHNH2 28.856
OMe 19.1 3-Py(C=O)-NHNH2 17.527
OAc 14.1 Hydroxylamine (NH, OH) Ph-NHNPh2 24.556
NMe2 19.8 EtO2C-NHNH2 22.256
Ph OH 2,4-(NO2)2PhNHNPh2
NO2 10.8 N 23.9 O=C(NHNH2)2 23.357 12.156
CF3 15.3
Cl 16.725 Bn S=C(NHNH2)2 16.657 4-CF3PhNHNH2 25.756
F 18.0 Ph OBn O
N 23.5 4-NC-PhNHNH2 25.156
NMe3+ 14.7
SO2Me 13.6 H N H 15.356
CN 13.2 PhNHOH 24.2 NPh Sulfonamide (NH)
O
OH Me-SO2-NH2 17.539
Hydroxamic Acid (NH,OH) N H
O N CF3-SO2-NH2 9.739
X 27
F 15.6 13.7 R Ph-SO2-NH2 16.127
Ph NHOH
OMe 17.8 O R=H 14.956
Ph-SO2-NHOH 15.457
Ac 14.8 18.027 R=Ph 15.256
CN 12.1 Ph NMeOH Me-SO2-NHPh 12.9
O O
NH2 18.2 Ph SO2-NHNH2 17.127
14.427
Ph NHOBn NH
OH O 12.756 Ph-SO2-NHNMe2 15.857
NH
16.027
Me NHOH NH
X O O O Ph-S-Me 24.3
X = Cl 15.825 19.627 O
F 15.825 Me NMeOH NH
13.256
CN 14.825 O
NH
NO2 14.425 17.127
Bu-t Me NHOMe
O

OH 16.8 Carboxylic Acids (OH)

Inorganic Acids
O
Bu-t 52 12.639
HCN 12.9
Me OH
HN3 7.952
O2N OH O
HF 15.52 11.142
5.1
HCl 1.852 OH
NO2
HO 52
O
HBr 0.9 O2N 9.1
16.2 NH4+ 10.552 OH
HOH 31.424 Sulfinic Acids (OH)
OH HON=O 7.552 O
17.2 NH3 (41) 19
S 7.1
Ph OH
H2N-CN 16.952
OH Sulfonic Acids (OH)
Me-SO2-OH 1.639
N 15.7
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022

Amidine (NH) Guanidine (NH) Pyridyl

NSO2Ph NSO2Ph
17.3 19.4
Me NH2 H2N NH2
NSO2Ph NH
15.0 28.541
Ph NH2 H2N NH2
NH 41
26.7
Ureas (NH)
Ph NH2
NH O
27.141 26.941
Me NH2 H2N NH2
O
19.541
PhHN NHPh
S
21.041
H2N NH2

Equilibrium pKa Table (DMSO Solvent and Reference)

References (Bordwell et al.)

1. J. Am. Chem. Soc. 1975, 97, 7006. 24. J. Org. Chem. 1980, 45, 3295. 47. Kolthoff J. Am. Chem. Soc. 1968, 90, 23.
2. J. Am. Chem. Soc. 1975, 97, 7160. 25. J. Org. Chem. 1984, 49, 1424. 48. Bausch J. Org. Chem. 1990, 55, 5806.
3. J. Am. Chem. Soc. 1975, 97, 442. 26. J. Am. Chem. Soc. 1995, 117, 602. 49. Alder Chem. Commun, 1995, 1267
4. J. Am. Chem. Soc. 1967, 89, 2752. 27. J. Org. Chem. 1995, 55, 3330. 50. J. Org. Chem. 1978, 43, 1763.
5. J. Org. Chem. 1976, 41, 1885. 28. J. Am. Chem. Soc. 1996, 118, 8777. 51. J. Org. Chem. 1991, 56, 4218.
6. J. Org. Chem. 1976, 41, 1883. 29. J. Org. Chem. 1996, 61, 4103. 52. Acc. Chem. Res. 1988, 21, 456, 463.
7. J. Org. Chem. 1976, 41, 2786. 30. J. Am. Chem. Soc. 1991, 113, 985. 53. J. Org. Chem. 1991, 56, 4448.
8. J. Org. Chem. 1976, 41, 2508. 31. J. Org. Chem. 1992, 57, 3019. 54. J. Am. Chem. Soc. 1988, 110, 2964.
9. J. Org. Chem. 1977, 42, 321. 32. J. Org. Chem. 1998, 63, 7574. 55. J. Am. Chem. Soc. 1974, 76, 1214.
10. J. Org. Chem. 1977, 42, 326. 33. J. Am. Chem. Soc. 1994, 116, 968 56. J. Am. Chem. Soc. 1997, 119, 9125.
11. J. Org. Chem. 1977, 42, 1817. 34. J. Am. Chem. Soc. 1989, 111, 7558 57. J. Org. Chem. 1990, 55, 3337.
12. J. Org. Chem. 1978, 43, 3113. 35. J. Am. Chem. Soc. 1992, 114, 7623 58. Can. J. Chem. 1990, 68, 1714.
13. J. Org. Chem. 1978, 43, 3095. 36. J. Am. Chem. Soc. 1994, 116, 973 59. Arnett J. Am. Chem. Soc. 19874, 109, 809.
14. J. Org. Chem. 1978, 43, 1764. 37. J. Org. Chem. 1988, 53, 780. 60. J. Phys. Org. Chem. 1988, 1, 209.
15. J. Org. Chem. 1980, 45, 3884. 38. J. Am. Chem. Soc. 1988, 110, 8520 61. Terrier J. Org. Chem. 2003, 68, 6566.
16. J. Org. Chem. 1980, 45, 3305. 39. J. Org. Chem. 1976, 41, 2507. 62. Courtet-Coupez Bull. Soc. Chim. Fr. 1969, 1033.
17. J. Org. Chem. 1980, 45, 3325. 40. J. Am. Chem. Soc. 1990, 112, 792 63. Curtis J. Am. Chem. Soc. 1969, 91, 6011
18. J. Org. Chem. 1981, 46, 4327. 41. J. Am. Chem. Soc. 1991, 113, 8398. 64. Crampton J. Chem. Res. (S) 1997, 22.
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21. J. Org. Chem. 1982, 47, 2504. 44. J. Org. Chem. 1993, 58, 3061. communication. For a review, see: F. G.
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 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated 4/11/2022
Equilibrium pKa Table (H2O Solvent and Reference)
Values outside the boxes were determined by approximate methods.

Oxygen Acids Nitrogen Acids Carbon Acids

+
CF3SO3H PH4 -14.
+ (O2N)2CH2 3.6 H
O C6H5-C≡N-H -10.5 O + -24.8
C6H5-N -12.4 +
+ H CH3
CH3-C≡N-H -10. 5.2
OH
NO2 H H
+ OH O
O 2N NH3 + -9.3 H
C6H5-C -7.8 O O
9.03 +
OH -24.3
NO2
C6H5 H N≡C-H 9.1
+ +
-6.5 C6H5-N -2.9
O H + H
N-C6H5 CH3N≡N 10.01
CH3 + -18.5
+ O2N-CH3 10.2 H3C CH3
(CH3)2S H -5.4 +
(C6H5)2NH2 0.8 O O CH3
+ 10.7
S H -4.4 + OEt + -12.5
CH3-PH3 2.7 H3C CH3
+ + (CF3)3CH 11.
(CH3)2O H -3.8 C6H5-NH3 4.6
O + (NC)2CH2 11.2
N H 5.2
CH3-S OH -2.6
O + O 12.26
N≡C-CH2CH2-NH3 7.9
+
CH3-OH2 -2.2 + O O
(CH3CH2)3P H 9.1 12.9
+ EtO OEt
O H -2.1 +
H2N N H 9.2
15.
+ -1.8 +
(CH3)2S=OH NH4 9.2
- + O
O N≡N-H 10.0
+ + CH3-C-H 16.7
N O H -1.4 CH3CH2NH3 10.6
O + O
(CH3CH2)2NH2 11.0 CH3-C-Ph 18.3
CF3-CO2H -0.3 +
(CH3CH2)3NH 10.8 O
NO2 CH3-C-CH3 19.3
O=N H 11.5
0.3 + 20
O 2N OH NH2
Ph 11.24
NO2 NH2
C6H5-CH2-C≡N 21
+ 2.6 + NH2
(CH3)2Se=OH C6H5-C≡C-H 23
(CH3)2N-C-N(CH3)2 13.6
C6H5-CO2H 4.2 CH3CO2Et 24
CH3CO2H 4.8 15. H-C≡C-H 24
N H
HOCO2H 6.3 CH3-C≡N 25
C6H5-SH 6.5
C6H5-NH2 28. 29
CH2=C(Ph)OH 8.02 H
((CH3)3Si)2N-H 30.
C6H5-OH 10.0 CF3-H 32
(i-C3H7)2N-H 36. O
HCO3 10.3
CH3-S CH3 33
RS-H 10.5 O
N H 37.
CH2=CHOH 10.5 (C6H5)3C-H 32
O
CH2=C(CH3)OH 10.9
11.7
Halogen Acids CH3-S CH3 33
HOOH
H-I -5.2 C6H5-CH3 41
H2O 14.010
H-Br -4.7
CH3-OH 16 44
H-Cl -2.2
(CH3)3C-OH 20
H-F 3.2 CH3CH3 50
 © 2021 ACS Division of Organic Chemistry
Author: Prof. Hans Reich Updated
Updated4/11/2022
4/7/2022

Gas Phase Acidities

δ∆H°acid (kcal/mol) 10 ∆H°acid (kcal/mol)

CH3-CH3 (420.1)2 420

Me2CH2 (419.4)2
CH4 (416.6)1 0
Me3CH (413.1)2
H
(408)7 410
FCH3 (409) 3 H
H2C=CH2 (409)8 -10
CH3OCH3 (407)3 PhCH2CH2-H (406)7

Ph-H (400.7)4 H2 (400.4)1

400
H NH3 (399.6)1
3 -20
ClCH3 (395.6) (398)
MeSCH3 (393.2)3
Me3SiCH3 (390.9)3 F2CH2 (389)7 390 HO-H (390.8)1
CH2C(O)-H (387)7
H2C=CH-CH3 (387.2)1 H -30
Me2PCH3 (384)3 (386.9)4
9 (383)8 Me3Si-H (383)2
CH2=C=CH2 (381.1) F
H 380
PhCH3 (379.0)1 F3CH (377)3 MeO-H (380.6)2

F3C-H (375.6)1 HC≡C-H (377)8 -40

HOO-H (376.5)6
6
Cl2CH2 (374.1)3 MeOO-H (374.6)
SiH4 (372.8)2
(Me3Si)2CH2 (373)3 F-H (371.5)1
CH3SOCH3 (372.7)1
(Me2P)2CH2 (370)3
370 PH3 (370.4)1
N≡CCH3 (369)7
-50 PhNH2 (367.1)1
CH3COCH3 (368.8)1 H
CH3SO2CH3 (366.6)1 Ph2CH2 (364.5)1 Me3Ge-H (361.5)2
(Ph)3C-H N
PhCOCH3 (363.2)1 (CH2=CH)2CH2 (359.7)5 360 (360.7)1 GeH4 (359)2

O2NCH3 (358.7)1 Cl3C-H (356.7)3 -60

(356.1)1 MeS-H (356.9)2
NC-H (353.1)1
Ph CN (348.7)5
PhO-H (351.4)1
350
HS-H (351.2)2
CF3COCH3 (347.1)5 Me3Sn-H (349)2
(348.5)5 -70
O O EtCO2H (345.2)5
(342.6)5
(CH3CO)2CH2 (342.6)5 340 PhS-H (338.9)1
O O HSe-H (338.7)1
PhCO2H (337.7)5 -80
5
(335.1) FCH2CO2H (335.6)5
ClCH2CO2H (333.6)5 Cl-H (333.3)1
5
(N≡C)2CH2 (331.7) 330
F2CHCO2H (328.4)5
-90

1. Bartmess J. Am. Chem. Soc. 1979, 101, 6046 Br-H (323.6)1

2. Braumann, J. Am. Chem. Soc. 1995, 117, 4905
3. Braumann J. Am. Chem. Soc. 1998, 120, 2919 320
4. Tetrahedron Lett. 1997, 0, 8519
5. Kebarle J. Am. Chem. Soc. 1976, 98, 3399 (add 3-4?) -100
6. Ellison I-H (314.3)1
7. Squires J. Am. Chem. Soc. 1990, 112, 2517
8. Kass J. Am. Chem. Soc. 2003, 125, 11746
310 2015-07
9. Review: Kass Chem. Rev. 2013, 113, 6986.
10. Meister Helv. Chim. Acta 2014, 97, 1.