Solvents used in organic chemistry are characterized by their physical characteristics.

Among the most important are whether the solvents are polar or non-polar, and whether
they are protic or aprotic.  Because non-polar solvents tend to be aprotic,the focus is
upon polar solvents and their structures. 

Solvent Polarity
Solvents are generally classified by the polarity, and considered either polar or non-
polar, as indicated by the dielectric constant.  However, as with many properties, the
polarity is a continuous scale, and the correct question is not "is it polar or non-polar"
but "how polar is it."  Nonetheless, guidelines have been created to make it easier.
Generally, solvents with dielectric constants greater than about 5 are considered "polar"
and those with dielectric constants less than 5 are considered "non-polar." 

Table 1: Examples of a few common solvents used in organic chemistry

Solvent Boiling Point, Dielectric

Celsius Constant

  NON-POLAR  
SOLVENTS

Pentane, C H 5 12 36 1.8

Hexane, C H
6 14 69 1.9

Benzene, C H 6 6 80 2.3

Chloroform, CHCl3 61 4.8

Diethyl ether, (CH CH ) O 3 2 2 35 4.3

1,40-Dioxane, cyc-(CH CH OCH CH O) 2 2 2 2 101 2.3

  POLAR PROTIC  
 SOLVENTS

Water, H O2 100 78.5

methanol, CH OH 3 65 32.6

ethanol, CH CH OH
3 2 78.5 24.3

isopropyl alcohol, CH CH(OH)CH 3 3 82 18

acetic acid, CH COOH 3 118 6

  POLAR APROTIC  
SOLVENTS

dichloromethane, CH Cl 2 2 40 9.1

tetrahydrofuran (THF), cyc-(CH ) O 2 4 66 7.5

ethyl acetate, CH C(O)OCH CH 3 2 3 77 6

acetonitrile, CH CN 3 81.6 37.5

dimethylformamide (DMF), HCON(CH ) 3 2 153 38

dimethyl sulfoxide (DMSO), CH SOCH 3 3 189 47

acetone, CH COCH 3 3 56.5 21

hexamethylphosphoric triamde (HMPT), 232 30

[(CH ) N] PO
3 2 3

Protic vs Aprotic Solvents
The table above distinguishes between protic and aprotic solvents. For the solvents
included in the table, the distinguishing feature is the presence of an -OH group, and
that is the most common characteristic of a protic solvent.  However, there are
exceptions, such as nitromethane, CH NO , which is also considered a protic solvent.
3 2

That might suggest that Bronsted acidity is the most important feature, because
nitromethane is very acidic, with a pKa of about 10. However, acetone is still considered
a polar aprotic solvent, despite the fact that it is relatively acidic, and not significantly
less acidic than alcohols. Then again, acetone (and other carbonyl containing solvents)
are, indeed, poor solvents when using strong bases due to their relatively high acidity.

Significance
Solvent properties are in important consideration in many chemical reactions, including
nucleophilic substitution reactions.  As strong hydrogen-bond donors, protic solvents are
very effective at stabilizing ions.  Therefore, they favor reactions in which ions are
formed, such as the S 1 reaction, and disfavor reactions where ions are reactants, such
N

as the S 2 reaction.
N

Polar protic solvents[edit]

Polar protic solvents are often used to dissolve salts. In general, these solvents have high
dielectric constants and high polarity.

Common characteristics of protic solvents :

 solvents display hydrogen bonding

 solvents have an acidic hydrogen (although they may be very weak acids such as ethanol)
 solvents dissolve salts
o cations by unshared free electron pairs
o anions by hydrogen bonding

Examples include water, most alcohols, formic acid, hydrogen fluoride, and ammonia. Polar
protic solvents are favorable for SN1 reactions, while polar aprotic solvents are favorable for SN2
reactions.

Polar aprotic solvents[edit]

Polar aprotic solvents are solvents that lack an acidic hydrogen. Consequently, they are not
hydrogen bond donors. These solvents generally have intermediate dielectric constants and
polarity. Although discouraging use of the term "polar aprotic", IUPAC describes such solvents
as having both high dielectric constants and high dipole moments, an example being acetonitrile.
Other solvents meeting IUPAC's criteria include DMF, HMPA, and DMSO.[1]

Common characteristics of aprotic solvents:

 solvents that can accept hydrogen bonds

 solvents do not have acidic hydrogen
 solvents dissolve salts

The criteria are relative and very qualitative. A range of acidities are recognized for aprotic
solvents. Their ability to dissolve salts depends strongly on the nature of the salt.

Polar aprotic solvents are generally incompatible with strong bases, such as Grignard reagents or
n-butyllithium. These reagents require ethers, not nitriles, amides, sulfoxides, etc.

Properties of common solvents[edit]

The solvents are qualitatively grouped into non-polar, polar aprotic, and polar protic solvents,
often ranked by dielectric constant.

Boiling Dielectric Dipole moment

Solvent Chemical formula Density
point constant (D)

Non-polar solvents

CH3-CH2-CH2-CH2-CH2-
Hexane 69 °C 2.0 0.655 g/mL 0.00 D
CH3

benzene C6H6 80 °C 2.3 0.879 g/ml 0.00 D

toluene C6H5CH3 111 °C 2.4 0.867 g/mL 0.36 D

1,4-dioxane (CH2CH2O)2 101 °C 2.3 1.033 g/mL 0.45 D

chloroform CHCl3 61 °C 4.8 1.498 g/mL 1.04 D

diethyl ether (CH3CH2)2O 35 °C 4.3 0.713 g/mL 1.15 D

1.3266
dichloromethane (DCM) CH2Cl2 40 °C 9.1 1.60 D
g/mL

Polar aprotic solvents

N-methylpyrrolidone CH3NC(O)C3H6 202 °C 32.2 1.028 g/mL 4.1 D

tetrahydrofuran (THF) C4H8O 66 °C 7.5 0.886 g/mL 1.75 D

ethyl acetate (EtOAc) CH3CO2CH2CH3 77 °C 6.0 0.894 g/mL 1.78 D

 acetone[note 1] CH3C(O)CH3 56 °C 21 0.786 g/mL 2.88 D

dimethylformamide
HC(O)N(CH3)2 153 °C 38 0.944 g/mL 3.82 D
(DMF)

acetonitrile (MeCN) CH3CN 82 °C 37 0.786 g/mL 3.92 D

dimethyl sulfoxide
CH3S(O)CH3 189 °C 47 1.092 g/mL 3.96 D
(DMSO)

propylene carbonate
C4H6O3 242 °C 64 1.205 g/mL 4.90 D
(PC)

Polar protic solvents

formic acid HCO2H 101 °C 58 1.21 g/mL 1.41 D

n-butanol CH3CH2CH2CH2OH 118 °C 18 0.810 g/mL 1.63 D

isopropanol (IPA) (CH3)2CH(OH) 82 °C 18 0.785 g/mL 1.66 D

100–103 ° 1.1371
nitromethane CH3NO2 35.87 3.56 D
C g/mL

ethanol (EtOH) CH3CH2OH 79 °C 24.55 0.789 g/mL 1.69 D

methanol (MeOH) CH3OH 65 °C 33 0.791 g/mL 1.70 D

Acetic acid (AcOH) CH3-CO2H 118 °C 6.2 1.049 g/mL 1.74 D

Water H2O 100 °C 80 1.000 g/mL 1.85 D

Acetone is subject to keto-enol tautomerism to propen-2-ol and can therefore exhibit a protic
note 1

behavior.

DAFTAR PUSTAKA

Wikipedia. 2018. Protic Solvent. https://en.wikipedia.org/wiki/Protic_solvent. Diakses : 16 Oktober

2018.